Herbicidal benzenesulfonamides

ABSTRACT

Sulfonylurea compounds which contain dihydroisobenzofuran, dihydroisobenzothiophene, or isoindoline 4-sulfonamide substituents such as 1,3-dihydro-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]benzo[c]furan-4-sulfonamide and their use as agricultural chemicals, including plant growth regulants and herbicides.

BACKGROUND OF THE INVENTION

This invention relates to novel sulfonylurea compounds and their use asagricultural chemicals, including plant growth regulants and herbicides.

U.S. Pat. Nos. 4,127,405, issued Nov. 28, 1978, and 4,169,719, issuedOct. 2, 1979, both patents to Levitt, discloseN-[(1,3,5-triazin-2-yl)aminocarbonyl]arylsulfonamides andN-(heterocyclicaminocarbonyl)arylsulfonamides, respectively, which areuseful as agricultural chemicals.

U.S. Pat. No. 4,348,220, issued Sept. 7, 1982 to Schwing disclosessulfonylurea compounds containing alkoxyalkyl substituents.

U.S. Ser. No. 410,993, filed Aug. 27, 1982, discloses benzofuran andbenzothiophene sulfonamides which are useful as agricultural chemicals.

SUMMARY OF THE INVENTION

This invention relates to novel compounds of Formula I, suitableagricultural compositions containing them and their method-of-use aspre-emergent or post-emergent herbicides or plant growth regulants.##STR1##

Q is O, S(O)_(n) or NR₃ ;

n is 0, 1 or 2;

R₁ is H, CH₃, Cl or F;

R₂ is H, Cl, Br, C₁ -C₃ alkoxy or CF₃ ;

R₃ is H or C₁ -C₄ alkyl;

R₄ is H or CH₃ ;

R₅ is H or CH₃ ;

R₆ is H, Cl or F;

R₇ is H, Cl or F;

R₈ is H, Cl or F;

R is H or CH₃ ;

A is ##STR2##

X is F, Cl, Br, C₁ -C₂ alkyl, C₁ -C₂ alkoxy, OCF₂ H or CF₃ ;

Y is H, NH₂, NHCH₃, N(CH₃)₂, C₁ -C₄ alkyl, C₁ -C₄ alkyl substituted with1-3 atoms of (a) F, (b) Cl or (c) Br, CH₂ OCH₃, CH₂ OC₂ H₅, C₁ -C₄alkoxy, C₁ -C₂ alkylthio, C₃ -C₄ alkenyloxy, C₃ -C₄ alkynyloxy, OCH₂ CH₂OCH₃, OCH₂ CH₂ F, OCH₂ CH₂ Cl, OCH₂ CH₂ Br, OCH₂ CF₃, CH(OCH₃)₂, CH(OC₂H₅)₂, ##STR3## or GCF₂ T;

G is O or S;

T is H, CHClF, CHBrF, CF₂ H or CHFCF₃ ;

Z is CH or N;

X₁ is O or CH₂ ;

Y₁ is H, CH₃, OCH₃ or Cl;

X₂ is CH₃, OCH₃ or SCH₃ ;

Y₂ is CH₃, C₂ H₅ or CH₂ CF₃ ;

X₃ is CH₃ or OCH₃ ; provided that:

(1) when X is F, Cl or Br, then Z is CH and Y is NH₂, NHCH₃, N(CH₃)₂,CH₃, OCH₃ or OCF₂ H; and

(2) when R₁ is F or Cl, when R₆, R₇ and R₈ are the same as R₁ and Q is Oor S; and when R₁ is H or CH₃, then R₆, R₇ and R₈ are H;

and their agriculturally suitable salts.

Preferred for their higher herbicidal activity, greater plant growthregulant activity and/or more favorable ease of synthesis are:

(1) Compounds of Formula 1 where L is L-1.

(2) Compounds of Preferred 1 where A is A-1.

(3) Compounds of Preferred 2 where R is H, R₁ is H and R₂ is H.

(4) Compounds of Preferred 3 where X is Cl, CH₃, OCH₃ or OCF₂ H and Y isCH₃, OCH₃, OCH₂ CH₃, CH₂ OCH₃, CH(OCH₃)₂ or GCF₂ T where G is O and T isH.

Specifically preferred for their highest herbicidal activity, greatestplant growth regulant activity and/or more favorable ease of synthesisare the following:

1,3-Dihydro-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]benzo[c]furan-4-sulfonamide,m.p. 190°-194° C. (d);

1,3-Dihydro-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]benzo[c]furan-4-sulfonamide,m.p. 225°-229° C. (d);

1,3-Dihydro-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]benzo[c]furan-4-sulfonamide,m.p. 199°-202° C. (d); and

1,3-Dihydro-N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]benzo[c]furan-4-sulfonamide,m.p. 202°-205° C. (d).

DETAILED DESCRIPTION OF THE INVENTION Synthesis

The compounds of this invention of Formula I, above, there Q is O, S orSO₂, can be prepared, as shown in Equation 1, by reaction of theappropriate sulfonyl isocyanate of Formula II, where Q is O, S or SO₂,with the appropriate amine of Formula III, where R and A are aspreviously defined in the Summary of the Invention above.

Equation 1 ##STR4##

The reaction of Equation 1 is most conveniently carried out by additionof a solution of the sulfonyl isocyanate II in an inert organic solventsuch as methylene chloride, acetonitrile, xylene or similar solvents toa solution or suspension of the amine III in the same solvent. Manycompounds of Formula I are insoluble in the reaction solvent, andprecipitate from it. They can be collected and purified by triturationwith, or crystallization from, an appropriate solvent.

Those compounds of Formula I which are soluble in the reaction solventcan be isolated by evaporation of the reaction solvent followed bytrituration with, or recrystallization from, an appropriate solvent.

The sulfonyl isocyanates of Formula II, where Q is O, S or SO₂, can beprepared from sulfonamides of Formula IV by the methods described inU.S. Pat. No. 4,379,769, issued Apr. 12, 1983 to Levitt (Equation 2).

Equation 2 ##STR5##

Compounds of Formula Ia, where Q is other than S(O), also can beprepared by reaction of a sulfonamide of Formula IV, where Q is otherthan S(O) with a carbamate of Formula V in the presence of at least onemolar equivalent of trimethylaluminum.

Equation 3 ##STR6##

The reaction of Equation 3 is carried out by addition oftrimethylaluminum to a solution or suspension of the sulfonamide ofFormula IV in an inert solvent such as methylene chloride,1,2-dichloroethane or toluene, followed by addition of the carbamate ofFormula V and heating of the reaction mixture at the boiling point ofthe solvent for periods of about 4 to 48 hours. The compounds of FormulaIa can be isolated by the addition of dilute acid, and, if insoluble inthe reaction solvent, the reaction products can be collected byfiltration. If the reaction products are soluble in the reactionsolvent, they can be isolated by evaporation of the solvent.Purification can be achieved by the methods described for Equation 1.

The compounds of Formula Ia where L and A are as previously defined, canalso be prepared, as shown in Equation 4, by the reaction of asulfonamide with a phenyl carbamate of Formula VI, by methods similar tothose described in South African Patent Application No. 825,671.

Equation 4 ##STR7##

The reactants are heated together, in the presence of an inorganic ororganic base, in an inert organic solvent, such as dioxane, toluene orsimilar solvents, for several hours. The compounds of Formula Ia can beisolated by concentration and/or evaporation of the solvent andpurification of the reaction product by methods previously described.

The compounds of Formula I, where L, R and A are as previously defined,can be prepared, as shown in Equation 5, by reaction of a sulfonylcarbamate of Formula VII and an amine of Formula III, by the methodsdescribed in South African Patent Application No. 825,042.

Equation 5 ##STR8##

The compounds of Formula I where Q is S(O) and R and A are as previouslydefined can also be prepared by oxidation, by methods well known tothose skilled in the art, of the compounds of Formula I where Q is S.

The sulfonamides of Formula IV can be prepared from the correspondingsulfonyl chlorides by methods well known in the art. When additionalchemical reactions are required in the synthesis of sulfonamides ofFormula IV, it is occasionally advantageous to convert the sulfonylchlorides of Formula VII to a N-tert-butyl sulfonamide of Formula IX,followed by removal of the tert-butyl group; when all chemicalmodifications are complete, as shown in Equation 6.

Equation 6 ##STR9##

The preparation of sulfonamides of Formula IX are well known to thoseskilled in the art. The removal of the tert-butyl group can be carriedout by (a) stirring a solution of the sulfonamide of Formula IX intrifluoroacetic acid for several hours, or (b) heating a solution ofsulfonamides IX in methanol which contains hydrogen chloride orconcentrated hydrochloric acid.

The sulfonyl chlorides of Formula VIII can be prepared by the methodsshown in Equations 7A and 7B, both of which are well known in the art.

Equation 7 ##STR10##

The amines of Formula III can be prepared by the methods described in(a) U.S. Pat. No. 4,339,267, (b) European Patent Application No. 46,677,(c) European Patent Application No. 73,562, (d) South African PatentApplication No. 825,405 and (e) Vol. XIII and Vol. XVI of "The Chemistryof Heterocyclic Compounds," a series published by IntersciencePublishers.

Agriculturally suitable salts of compounds of Formula I are also usefulherbicides and can be prepared in a number of ways known to the art. Forexample, metal salts can be made by treating compounds of Formula I witha solution of alkali or alkaline earth metal salt having a sufficientlybasic anion (e.g., hydroxide, alkoxide, carbonate or hydride).Quaternary amine salts can be made by similar techniques.

Salts of compounds of Formula I can also be prepared by exchange of onecation for another. Cationic exchange can be effected by direct contactof an aqueous solution of a salt of a compound of Formula I (e.g.,alkali metal or quaternary amine salt) with a solution containing thecation to be exchanged. This method is most effective when the desiredsalt containing the exchanged cation is insoluble in water, e.g., acopper salt, and can be separated by filtration.

Exchange may also be effected by passing an aqueous solution of a saltof a compound of Formula I (e.g., an alkali metal or quaternary aminesalt) through a column packed with a cation exchange resin containingthe cation to be exchanged. In this method, the cation of the resin isexchanged for that of the original salt and the desired product iseluted from the column. This method is particularly useful when thedesired salt is water-soluble, e.g., a potassium, sodium or calciumsalt.

Acid addition salts, useful in this invention, can be obtained byreacting a compound of Formula I with a suitable acid, e.g.,p-toluenesulfonic acid, trichloroacetic acid or the like.

The compounds of this invention are further illustrated by the followingexamples, wherein temperatures are given in degrees centigrade and partsare by weight unless otherwise indicated.

EXAMPLE 1 1,3-Dihydro-4-nitrobenzo[c]furan

A. A mixture of 100.0 g of methyl 2-methyl-3-nitrobenzoate, 100.0 g ofN-bromosuccinimide, 3.0 g of dibenzoyl peroxide and 1000 ml of carbontetrachloride was refluxed for 24 hours. The reaction mixture wascooled, 3.0 g of dibenzoyl peroxide added, and refluxing continued anadditional 24 hours. The reaction mixture was cooled, filtered and thefiltrate concentrated in vacuo. The crude reaction product was dissolvedin ether and the organic solution washed sequentially with saturatedsodium sulfite (500 ml), water (2×500 ml), 2.5% sodium hydroxide (500ml), water (2×500 ml) and saturated brine (500 ml). The organic solutionwas dried over magnesium sulfate, filtered and the solvent evaporated invacuo giving a pale yellow oily solid. Recrystallization from 350 ml of1-chlorobutane/cyclohexane (2:1) gave 73.9 g of methyl2-bromomethyl-3-nitrobenzoate, m.p. 67°-70°.

B. A solution of 54.8 g of methyl 2-bromomethyl-3-nitrobenzoate in amixture of 200 ml dioxane and 45 ml water was refluxed for 72 hours. Thereaction solution was cooled and concentrated in vacuo. The resultingsolid was slurried in water, collected, washed with water and dried.Recrystallization from 1-chlorobutane gave 21.4 g of1,3-dihydro-4-nitrobenzo[c]furan-1-one, m.p. 133.5°-136°.

C. A suspension of 19.5 g of 1,3-dihydro-4-nitrobenzo[c]furan-1-one in100 ml of boron trifluoride etherate was cooled to 0°-5° under nitrogen.125 ml of a 1M solution of borane-tetrahydrofuran complex was addeddropwise below 10°. The orange suspension was allowed to warm to ambienttemperature (H₂ evolution), and the reaction mixture exothermed to 30°.When the exotherm subsided (15-20 minutes), the mixture was refluxed 2.5hours. The reaction mixture was cooled, decanted from some brown solids,and concentrated in vacuo to a yellow oil. The oil was cooled in an icebath and acidified with dilute hydrochloric acid (H₂ evolution), thendiluted with 300 ml water, and the suspension was extracted with ether.The organic solution was washed with brine, dried over magnesiumsulfate, filtered, and the solvent evaporated in vacuo. The resultingyellow solid was purified by chromatography, eluting with methylenechloride to give 15.4 g of 1,3-dihydro-4-nitrobenzo[c]furan as a paleyellow solid, m.p. 104°-108°.

NMR (CDCl₃) δ: 5.15 (t, 2H, CH₂); 5.40 (t, 2H, CH₂); 7.3-7.7 (m, 2H,aromatic); and 8.0-8.3 (m, 1H, aromatic).

EXAMPLE 2 1,3-Dihydrobenzo[c]furan-4-amine

A solution of 66.8 g of tin (II) chloride dihydrate in 150 ml ofconcentrated hydrochloric acid was cooled to 10°-15° and 14.9 g of1,3-dihydro-4-nitrobenzo[c]furan was added portionwise. The yellowsuspension was allowed to warm to 25° at which temperature a slowexotherm occurred. The reaction mixture was maintained at 45° by coolingfor 0.75 hour. The white suspension was cooled to 0°, the solid wascollected, washed with cold concentrated hydrochloric acid and ethylacetate giving 24.1 g of crude 1,3-dihydrobenzo[c]furan-4-aminehydrochloride, m.p. >250°.

A 2.0 g portion of the crude hydrochloride salt was dissolved in 50 mlwater and the solution made strongly alkaline with 10% sodium hydroxide.The aqueous mixture was extracted with ether. The organic solution waswashed with brine, dried over magnesium sulfate, and filtered. Thesolvent was evaporated in vacuo to give 0.5 g of1,3-dihydrobenzo[c]furan-4-amine, m.p. 85°-89°.

IR(nujol mull): NH₂ (3365 and 3400 cm⁻¹).

NMR (CDCl₃) δ: 3.5 (broad s, 2H, NH₂); 5.0 (m, 4H, CH₂); and 6.5-7.3 (m,3H, aromatic).

EXAMPLE 3 1,3-Dihydrobenzo[c]furan-4-sulfonamide

A. A suspension of 22.1 g of the crude hydrochloride salt prepared inExample 2 in a mixture of 30 ml of concentrated hydrochloric acid and 30ml acetic acid was cooled to 0°-5°. A solution of 6.2 g of sodiumnitrite in 15 ml water was added dropwise at 0°-5°. The thick suspensionwas diluted with 19 ml of concentrated hydrochloric acid to facilitatestirring and 1.0 g of sodium nitrite was added; stirring was continuedfor 1 hour. The suspension of the diazonium salt was added portionwiseat 0°-5° to a stirred mixture of 80 ml of acetic acid, 25 ml of sulfurdioxide and 1.6 g of copper (II) chloride dihydrate. The resulting palegreen suspension was allowed to warm to ambient temperature and stirredfor 4.5 hours. The yellow-green solution was poured into 1000 ml of coldwater and the aqueous mixture extracted three times with 1-chlorobutane.The combined organic solution was washed three times with water andsaturated sodium bicarbonate solution, then dried over magnesiumsulfate, and filtered. Evaporation of the solvent in vacuo gave 9.8 g of1,3-dihydrobenzo[c]furan-4-sulfonyl chloride as a yellow oil whichcrystallized on cooling and scratching, m.p. 40°-43°.

NMR (CDCl₃) δ: 5.15 (t, 2H, CH₂); 5.40 (t, 2H, CH₂); and 7.15-8.10 (m,3H, aromatic).

B. A solution of 9.8 g of the sulfonyl chloride, prepared in Part A, in150 ml tetrahydrofuran was cooled to approximately 5°, and 6.6 ml ofconcentrated ammonium hydroxide was added dropwise. The resulting yellowsuspension was allowed to warm to ambient temperature and stirred 0.5hour; thin-layer chromatography showed the reaction was complete. Thesolvent was evaporated in vacuo and the resulting solid was slurried in150 ml water, collected, washed with water and dried. The crude productwas washed with 1-chlorobutane and dried to give 7.74 g of1,3-dihydrobenzo[c]furan-4-sulfonamide, m.p. 153°-158°.

IR(nujol mull): SO₂ NH₂ (3260 and 3380 cm⁻¹).

NMR (CDCl₃ /DMSO-d₆)δ: 5.00 (t, 2H, CH₂); 5.23 (t, 2H, CH₂); 7.07 (broads, 2H, NH₂); and 7.30-7.93 (m, 3H, aromatic).

EXAMPLE 4 1,3-Dihydrobenzo[c]furan-4-sulfonyl isocyanate

A mixture of 7.0 g of 1,3-dihydrobenzo[c]furan-4-sulfonamide, 4.0 ml ofbutyl isocyanate, 0.1 g of DABCO® and 150 ml xylene was heated toreflux. Phosgene (3.1 ml) was added in small portions to the reactionmixture while maintaining the reaction temperature >130°. When additionof phosgene was complete, the reaction mixture was heated to reflux(128°) for 1 hour, then cooled under nitrogen. The reaction mixture wasfiltered under nitrogen, and the filtrate was concentrated in vacuo togive 1,3-dihydrobenzo[c]furan-4-sulfonyl isocyanate as an amber oil. Thecrude sulfonyl isocyanate was dissolved in methylene chloride (totalvolume=28 ml) for reaction with amino heterocycles.

IR(neat): SO₂ NCO (2215 cm⁻¹).

EXAMPLE 51,3-Dihydro-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]benzo[c]furan-4-sulfonamide

A 7.0 ml portion of the methylene chloride solution of1,3-dihydrobenzo[c]furan-4-sulfonyl isocyanate prepared in Example 4 wasadded to a stirred suspension of 0.78 g of4-methoxy-6-methylpyrimidin-2-amine in 20 ml of methylene chloride.After several minutes the amine dissolved, followed by formation of aprecipitate. After stirring for 1.75 hours, the solid was collected,washed with methylene chloride and 1-chlorobutane, then dried to give1.4 g of1,3-dihydro-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]benzo[c]furan-4-sulfonamide,m.p. 190°-194° (d).

IR(nujol null): C═O (1725 cm⁻¹).

NMR (CDCl₃ /TFA)δ: 2.6 (s, 3H, CH₃); 4.1 (s, 3H, OCH₃); 5.15 (broad s,2H, CH₂); 5.45 (broad s, 2H, CH₂); 6.6 (s, 1H, pyrimidine CH); 7.5-7.8(m, 2H, aromatic); and 7.8-8.2 (m, 1H, aromatic).

EXAMPLE 6 4-Nitrobenzo[c]thiophene-1(3H)-one

A. To a solution of 34.7 g of sodium methoxide in 600 ml methanol wasadded 57.9 g of 1,1-dimethylethanethiol below 25°. The resultingsolution was stirred one hour before the portionwise addition of 172.7 gof methyl 2-bromomethyl-3-nitrobenzoate. The resulting suspension wasrefluxed two hours. The mixture was cooled, and the solvent evaporatedin vacuo. The residual oil was partitioned between ether and water. Theorganic solution was washed twice with 2.5% sodium hydroxide solution,twice with water, followed by brine, then dried over magnesium sulfate,filtered and the filtrate concentrated in vacuo to give 164.2 g of crudemethyl 2-[(1,1-dimethylethylthio)methyl]-3-nitrobenzoate as an oil.

B. A mixture of 149.2 g of the crude oil prepared in Part A, 40 g ofp-toluenesulfonic acid and 500 ml of xylene was refluxed for 50 minutes.The dark brown soluution was cooled and the solvent evaporated in vacuo.Trituration of the resulting oil with ethanol gave a solid which wascollected, washed twice with ethanol followed by hexane, then dried togive 65.4 g of 4-nitrobenzo[c]thiophene-1(3H)-one, m.p. 128°-133°.

IR(nujol mull): C═O (1660 cm⁻¹).

NMR (CDCl₃)δ: 4.85 (s, 2H, CH₂); and 7.52-8.65 (m, 3H, aromatic).

EXAMPLE 71,3-Dihydro-N-(1,1-dimethylethyl)-1-oxobenzo[c]thiophene-4-sulfonamide

A. 4-Nitrobenzo[c]thiophene-1(3H)-one (38.1 g) was added portionwise toa solution of 146.0 g of stannous chloride dihydrate in 325 mlconcentrated hydrochloric acid. A slow exotherm from 18° to 42° occurredand the reaction mixture was maintained at 40°-45° by cooling. When theexotherm subsided, the suspension was stirred while cooling to ambienttemperature (3.5 hours). The solid was collected, washed with a smallvolume of cold concentrated hydrochloric acid, then dried under nitrogento give 57.7 g of crude 1,3-dihydro-1-oxobenzo[c]thiophene-4-aminehydrochloride, m.p. 205° (d).

B. A suspension of 57.7 g of the crude amine hydrochloride (prepared inPart A) in a mixture of 130 ml concentrated hydrochloric acid and 80 mlof acetic acid was cooled to 0°-5°. A solution of 14.9 g of sodiumnitrite in 40 ml of H₂ O was added dropwise at 0°-5°. The thick yellowsuspension was stirred approximately 0.25 hour, then added portionwiseto a stirred mixture of 65 ml of sulfur dioxide, 4.2 g of cupricchloride dihydrate, and 210 ml of acetic acid while keeping the reactiontemperature at 5°-10°. The yellow-green suspension was allowed to warmto ambient temperature and stirred 2.5 hours. The reaction suspensionwas poured into 5000 ml H₂ O; the solid was collected and washed twicewith water. The crude product was dissolved in methylene chloride; theorganic solution was dried over magnesium sulfate, filtered andconcentrated in vacuo. The product was slurried in hexane, collected anddried to give 34.3 g of 1,3-dihydro-1-oxobenzo[c]thiophene sulfonylchloride, m.p. 137°-140° (d).

IR(nujol mull): C═O (1680 cm⁻¹).

NMR (CDCl₃ /TFA)δ: 5.0 (s, 2H, CH₂); 7.65-8.10 (m, 1H, aromatic); and8.17-8.35 (m, 2H, aromatic).

C. A solution of 34.3 g of the sulfonyl chloride (prepared in Part B) in500 ml tetrahydrofuran was cooled to 20° and 21.2 g of1,1-dimethylethylamine was added dropwise below 25°. The yellowsuspension was stirred at ambient temperature until thin-layerchromatography showed the reaction was complete. The amine hydrochloridewas removed by filtration and washed with tetrahydrofuran. The combinedfiltrates were concentrated in vacuo to a yellow-brown oil whichpartially crystallized. The crude reaction product was partitionedbetween water and ether. The organic phase was washed with water andbrine, then stirred with magnesium sulfate and charcoal and filteredthrough Celite®. Concentration in vacuo of the filtrate gave an oilwhich crystallized on trituration with hexane. Recrystallization fromcyclohexane/1-chlorobutane gave 31.5 g of1,3-dihydro-N-(1,1-dimethylethyl)-1-oxobenzo[c]thiophene-4-sulfonamide,m.p. 121°-124°.

IR(nujol mull): NH (3295 cm⁻¹), C═O (1700 cm⁻¹).

NMR (CDCl₃)δ: 1.25 (s, 9H, t-Bu); 4.80 (s, 2H, CH₂); 5.48 (2, 1H, NH);and 7.57-8.40 (m, 3H, aromatic).

EXAMPLE 81,3-Dihydro-N-(1,1-dimethylethyl)benzo[c]thiophene-4-sulfonamide

A suspension of 8.0 g of1,3-dihydro-N-(1,1-dimethylethyl)-1-oxobenzo[c]thiophene-4-sulfonamidein a mixture of 15 ml of tetrahydrofuran, 25 ml of boron trifluorideetherate was cooled to 10° under N₂, and 56 ml of a 1M solution ofborane tetrahydrofuran complex was added dropwise at approximately 10°.The reaction mixture was allowed to warm to ambient temperature as a gaswas evolved. When ambient temperature was reached, a slow exotherm to31° occurred. When the exotherm subsided, the reaction mixture washeated to reflux for two hours, then cooled and allowed to standovernight. The supernatant was decanted fom some brown solid, andconcentrated in vacuo. The resulting yellow oil was cooled toapproximately 5°, acidified with 5% hydrochloric acid (gas evolution),and diluted with 150 ml water. The aqueous mixture was extracted withethyl acetate. The organic solution was washed twice with water, driedover magnesium sulfate, then filtered and the filtrate concentrated invacuo. The resulting yellow oil was purified by chromatography, usingmethylene chloride as eluent, to give 3.6 g of1,3-dihydro-N-(1,1-dimethylethyl)benzo[c]thiophene-4-sulfonamide, m.p.128.5°-132°.

IR(nujol mull): NH (3310 cm⁻¹).

NMR (CDCl₃)δ: 1.2 (s, 9H, t-Bu); 4.23 (m, 2H, CH₂); 4.52 (m, 2H, CH₂);5.22 (s, 1H, NH); 7.28-7.6 (m, 2H, aromatic); and 7.75-8.08 (m, 1H,aromatic).

EXAMPLE 9 1,3-Dihydrobenzo[c]thiophene-4-sulfonamide

A solution of 3.0 g of1,3-dihydro-N-(1,1-dimethylethyl)benzo[c]thiophene-4-sulfonamide in 50ml of trifluoroacetic acid was stirred at ambient temperature for 4hours. The brown solution was concentrated in vacuo. 1-Chlorobutane wasadded to the resulting brown oil and the mixture concentrated in vacuo.Repeating this procedure gave an oil which on trituration with1-chlorobutane gave a brown solid. Purification of the crude reactionproduct by chromatography, using hexane/ethyl acetate (3:2) as eluentgave 1.4 g of 1,3-dihydrobenzo[c]thiophene-4-sulfonamide as a paleyellow solid, m.p. 146°-148°.

IR(nujol mull): NH₂ (3270 and 3370 cm⁻¹).

NMR (CDCl₃ /DMSO-d₆)δ: 4.19 (m, 2H, CH₂); 4.5 (m, 2H, CH₂); 6.8 (broads, 2H, NH₂); and 7.2-8.0 (m, 3H, aromatic).

EXAMPLE 10 1,3-Dihydrobenzo[c]thiophene-4-sulfonyl isocyanate

A mixture of 5.5 g of 1,3-dihydrobenzo[c]thiophene-4-sulfonamide, 2.5 gof butyl isocyanate and 0.05 g of DABCO® in 50 ml of xylene was heatedto 135° and 2.2 ml of liquid phosgene was added in small portions atapproximately 135°. When the addition of phosgene was complete, heatingwas continued for 5 minutes before the dark brown suspension was cooledto ambient temperature under a slow stream of nitrogen. The reactionmixture was filtered under nitrogen and the filtrate was concentrated invacuo to give 1,3-dihydrobenzo[c]thiophene-4-sulfonyl isocyanate as adark red-brown oil. The crude sulfonyl isocyanate was dissolved inmethylene chloride (total volume=26 ml) for reaction withaminoheterocycles.

IR(neat): SO₂ NCO (2200 cm⁻¹).

EXAMPLE 111,3-Dihydro-N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]benzo[c]thiophene-4-sulfonamide

A 4.5 ml portion of the methylene chloride solution prepared in Example10 was added to a stirred suspension of 0.41 g of4,6-dimethoxy-1,3,5-triazin-2-amine in 5 ml of methylene chloride, andthe suspension stirred 2.5 days. The light purple solid was collected,washed with 1-chlorobutane and dried giving 0.91 g of1,3-dihydro-N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)]benzo[c]thiophene-4-sulfonamide,m.p. 190°-194° (d).

IR(nujol mull): C═O (1728 cm⁻¹).

NMR (CDCl₃ /DMSO-d₆)δ: 4.0 (s, 6H, OCH₃); 4.25 (broad s, 2H, CH₂); 4.55(broad s, 2H, CH₂); 7.1-8.2 (m, 4H, aromatic and NH); and 11.85 (broads, 1H, NH).

EXAMPLE 121,3-Dihydro-N-(1,1-dimethylethyl)benzo[c]thiophene-4-sulfonamide2,2-dioxide

A solution of 6.8 g of1,3-dihydro-N-(1,1-dimethylethyl)benzo[c]thiophene-4-sulfonamide in 100ml of acetic acid was warmed to 75°-80°, and 5.4 ml of 30% hydrogenperoxide was added dropwise. The reaction mixture was heated at 75°-80°for 1 hour, 2.0 ml of 30% hydrogen peroxide added, and heating continuedfor 1 hour at approximately 90°. The reaction solution was cooled toambient temperature, and the suspension poured into 600 ml water. Thesolid was collected, washed with water and dried giving 5.9 g of1,3-dihydro-N-(1,1-dimethylethyl)benzo[c]thiophene-4-sulfonamide2,2-dioxide, m.p. 170° (s), 178° (d).

IR(nujol mull): NH (3255 cm⁻¹).

NMR (CDCl₃ /DMSO-d₆)δ: 1.18 (s, 9H, t-C₄ H₉); 4.40 (s, 2H, CH₂); 4.73(s, 2H, CH₂); 7.35 (s, 1H, NH); 7.47-7.70 (m, 2H, aromatic); and7.85-8.13 (m, 1H, aromatic).

EXAMPLE 13 1,3-Dihydrobenzo[c]thiophene-4-sulfonamide 2,2-dioxide

A solution of 5.9 g of the compound, prepared in Example 12, in 65 ml oftrifluoroacetic acid was stirred at ambient temperature for 1.25 hours.The solvent was evaporated; 1-chlorobutane was added to the residualoil, and the mixture was concentrated. This process was repeated withethyl acetate. The crude reaction product was triturated with a warmmixture of 1-chlorobutane and ethyl acetate. The solid was collected,washed with 1-chlorobutane and dried to give 4.6 g of1,3-dihydrobenzo[c]thiophene-4-sulfonamide 2,2-dioxide, m.p. 174.5°-178°(d).

IR(nujol mull): SO₂ NH₂ (3270 and 3370 cm⁻¹).

NMR (CDCl₃ /DMSO-d₆)δ: 4.40 (s, 2H, CH₂); 4.75 (s, 2H, CH₂); 7.3 (s, 2H,NH₂); and 7.5-8.15 (m, 3H, aromatic).

EXAMPLE 141,3-Dihydro-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]benzo[c]thiophene-4-sulfonamide2,2-dioxide

A suspension of 0.74 g of the sulfonamide prepared in Example 13 in 50ml of methylene chloride was cooled to 10° to 15° under nitrogen, and1.17 ml of a 2M solution of trimethylaluminum in toluene was addedslowly. The suspension was allowed to warm to room temperature, 0.67 gof methyl N-(4,6-dimethoxypyrimidin-2-yl)carbamate was added, and thereaction mixture was heated at reflux overnight. The turbid solution wascooled to 0°-5° and 50 ml of 5% hydrochloric acid was added dropwise.The two-phase suspension was allowed to warm to ambient temperature,then filtered. The solid was washed with 1-chlorobutane and dried giving0.31 g of1,3-dihydro-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]benzo[c]thiophene-4-sulfonamide,2,2-dioxide, m.p. 170°-173° (d).

IR(nujol mull): C═O (1730 cm⁻¹).

NMR (CDCl₃)δ: 3.95 (s, 6H, OCH₃); 4.39 (s, 2H, CH₂); 4.89 (s, 2H, CH₂);5.8 (s, 1H, pyrimidine CH); 7.6 (m, 2H, aromatic); and 8.15 (m, 1H,aromatic).

EXAMPLE 15N-(1,1-Dimethylethyl)-2-methyl-2,3-dihydro-1,3-dioxo-1H-isoindole-4-sulfonamide

A. Phenylmethanethiol (43.4 g) was added to a solution of 22.9 g of85.6% potassium hydroxide in 300 ml of methanol. The solution wasstirred approximately 15 minutes and concentrated in vacuo. The salt wasdissolved in 200 ml of dimethylformamide and added dropwise to asolution of 72.1 g of 2-methyl-4-nitroisoindole-1,3-(2H)-dione in 200 mldimethylformamide, keeping the reaction temperature approximately 25° bycooling. The reaction mixture was stirred 2.25 hours at ambienttemperature and then poured into 4000 ml cold water. The pale yellowsolid was collected, washed twice with water followed by ethanol anddried to give 94.1 g of2-methyl-4-(phenylmethylthio)-1H-isoindole-1,3-(2H)-dione, m.p.180°-187°.

B. A suspension of 78.5 g of the compound prepared in Part A in 750 mlacetic acid and 50 ml water was cooled to 5°-10° and 44.3 ml of liquidchlorine was added dropwise below 15°. The suspension was stirred 0.5hour at approximately 10°, then poured into 2000 ml water. The solid wascollected, washed twice with water followed by a mixture ofhexane/1-chlorobutane (1:1) and dried to give 66.9 g of1,3-dioxo-2,3-dihydro-2-methyl-1H-isoindole-4-sulfonyl chloride, m.p.159°-162.5°.

IR(nujol mull): C═O (1715 and 1770 cm⁻¹).

NMR (CDCl₃)δ: 3.27 (s, 3H, NCH₃); and 7.75-8.50 (m, 3H, aromatic).

C. 16.1 g of 1,1-Dimethylethylamine in 50 ml of tetrahydrofuran wasadded dropwise to a solution of 25.9 g of the sulfonyl chloride preparedin Part B in 300 ml of tetrahydrofuran. The addition caused the reactiontemperature to rise to 40°. The suspension was stirred 3 hours atambient temperature, then filtered, and the filtrate concentrated invacuo. Recrystallization of the crude product from 1-chlorobutane gave19.2 g ofN-(1,1-dimethylethyl)-2,3-dihydro-1,3-dioxo-2-methyl-1H-isoindole-4-sulfonamide,m.p. 160°-163°.

IR(nujol mull): NH (3260 cm⁻¹)

NMR (CDCl₃)δ: 1.27 (s, 9H, t-C₄ H₉); 3.13 (s, 3H, NCH₃); 6.55 (broad s,1H, NH); and 7.70-8.37 (m, 3H), aromatic).

EXAMPLE 162,3-Dihydro-N-(1,1-dimethylethyl)-2-methyl-1H-isoindole-4-sulfonamide-boranecomplex

A solution of 14.8 g of the compound prepared in Example 15 in 200 mltetrahydrofuran was cooled to 5°-10° under nitrogen, and 200 ml of a 1Msolution of borane-tetrahydrofuran complex was added dropwise. Thereaction solution was allowed to warm to ambient temperature, and thenheated slowly to reflux (gas evolution). The reaction mixture wasrefluxed overnight during which time a light yellow suspension formed.The reaction mixture was cooled to below 15°, 75 ml of water was addedcautiously (gas evolution), and the reaction mixture was concentrated invacuo. The oily solid was partitioned between water and ether. Theorganic phase was washed with water and brine, dried over magnesiumsulfate, filtered and the solvent evaporated in vacuo. The crudereaction product was slurried in 1-chlorobutane. The solid wascollected, washed with 1-chlorobutane and dried to give 8.5 g of2,3-dihydro-N-(1,1-dimethylethyl)-2-methyl-1H-isoindole-4-sulfonamide-boranecomplex; m.p. 140°-143° (d).

IR(nujol mull): NH (3320 cm⁻¹), BH₃ (2280, 2330, 2370 cm⁻¹).

NMR (CDCl₃)δ: 1.23 (s, 9H, t-C₄ H₉); 2.84 (s, 3H, NCH₃); 4.0-5.05 (m,5H, CH₂ and NH); and 7.45-8.0 (m, 3H, aromatic).

EXAMPLE 17 2,3-Dihydro-2-methyl-1H-isoindole-4-sulfonamide hydrochloride

A suspension of 5.3 g of the compound prepared in Example 16 in 20 ml ofmethanol was cooled to 10° and 50 ml of concentrated hydrochloric acidwas added dropwise at 10°-15° (gas evolution). The reaction mixture wasallowed to warm to room temperature and then refluxed 3.75 hours. Thereaction solution was cooled and concentrated in vacuo. The white solidwas washed with ethanol followed by ethyl acetate then dried to give 4.1g of 2,3-dihydro-2-methyl-1H-isoindole-4-sulfonamide hydrochloride, m.p.>250°.

IR(nujol mull): NH₂ (3150 and 3220 cm⁻¹).

NMR (DMSO-d₆): 3.0 (s, 3H, NCH₃); 4.63 (broad s, 2H, CH₂); 4.8 (broad s,2H, CH₂); 7.6-8.2 (m, 5H, aromatic and NH₂); and 13.6 (broad s, 1H,N.sup.⊕ -H).

                                      TABLE I                                     __________________________________________________________________________     ##STR11##                                                                    Q     R.sub.1                                                                          R.sub.2                                                                             R  X    Y          m.p. (°C.)                           __________________________________________________________________________    O     H  H     H  CH.sub.3                                                                           OCH.sub.3  190-194° (d)                         O     H  H     H  OCH.sub.3                                                                          OCH.sub.3  225-229° (d)                         O     H  H     H  CH.sub.3                                                                           CH.sub.3                                               O     H  H     H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                              O     H  H     H  OC.sub.2 H.sub.5                                                                   CH.sub.3                                               O     H  H     H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                              O     H  H     H  Cl   OCH.sub.3                                              O     H  H     H  Br   OCH.sub.3                                              O     H  H     H  F    OCH.sub.3                                              O     H  H     H  OCF.sub.2 H                                                                        CH.sub.3                                               O     H  H     H  OCF.sub.2 H                                                                        OCH.sub.3                                              O     H  H     H  OCF.sub.2 H                                                                        OCF.sub.2 H                                            O     H  H     H  OCF.sub.2 H                                                                        CF.sub.3                                               O     H  H     H  CF.sub.3                                                                           CF.sub.3                                               O     H  H     H  CF.sub.3                                                                           OCH.sub.3                                              O     H  H     H  CF.sub.3                                                                           OC.sub.2 H.sub.5                                       O     H  H     H  OCH.sub.3                                                                          H                                                      O     H  H     H  OCH.sub.3                                                                          NH.sub.2                                               O     H  H     H  OCH.sub.3                                                                          NHCH.sub.3                                             O     H  H     H  OCH.sub.3                                                                          N(CH.sub.3).sub.2                                      O     H  H     H  OCH.sub.3                                                                          n-C.sub.4 H.sub.9                                      O     H  H     H  OCH.sub.3                                                                          CH.sub.2 OCH.sub.3                                     O     H  H     H  OCH.sub.3                                                                          CH.sub.2 OC.sub.2 H.sub.5                              O     H  H     H  CH.sub.3                                                                           Oi-C.sub.3 H.sub.7                                     O     H  H     H  CH.sub.3                                                                           On-C.sub.4 H.sub.9                                     O     H  H     H  CH.sub.3                                                                           OCH.sub.2 CHCH.sub.2                                   O     H  H     H  CH.sub.3                                                                           OCH.sub.2 CCH                                          O     H  H     H  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OCH.sub.3                           O     H  H     H  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 F                                   O     H  H     H  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 Cl                                  O     H  H     H  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 Br                                  O     H  H     H  CH.sub.3                                                                           CH(OCH.sub.3).sub.2                                    O     H  H     H  CH.sub.3                                                                           CH(OC.sub.2 H.sub.5).sub.2                             O     H  H     H  CH.sub.3                                                                           OCH.sub.2 C(CH.sub.3)CH.sub.2                          O     H  H     H  CH.sub.3                                                                           OCH.sub.2 CCCH.sub.3                                   O     H  H     H  OCH.sub.3                                                                          SCH.sub.3                                              O     H  H     H  OCH.sub.3                                                                          SC.sub.2 H.sub.5                                       O     H  H     H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                    O     H  H     H  OCH.sub.3                                                                          CH(OC.sub.2 H.sub.5).sub.2                              O    H  H     H  OCH.sub.3                                                                           ##STR12##                                              O    H  H     H  OCH.sub.3                                                                           ##STR13##                                              O    H  H     H  OCH.sub.3                                                                          CH.sub.2 Cl                                            O     H  H     H  OCH.sub.3                                                                          SCF.sub.2 H                                            O     H  H     H  CH.sub.3                                                                           OCF.sub.2 CF.sub.2 H                                   O     H  H     H  CH.sub.3                                                                           OCF.sub.2 CHCF                                         O     H  H     H  CH.sub.3                                                                           OCF.sub.2 CHBrF                                        O     H  H     H  CH.sub.3                                                                           OCF.sub.2 CHFCF.sub.3                                  O     H  H     H  CH.sub. 3                                                                          OCH.sub.2 CF.sub.3                                     O     CH.sub.3                                                                         H     H  OCH.sub.3                                                                          OCH.sub.3                                              O     H  Cl    H  CH.sub.3                                                                           OCH.sub.3                                              O     H  Br    H  CH.sub.3                                                                           OCH.sub.3                                              O     H  OCH.sub.3                                                                           H  OCH.sub.3                                                                          OCH.sub.3                                              O     H  OC.sub.2 H.sub.5                                                                    H  OCH.sub.3                                                                          OCH.sub.3                                              O     H  On-C.sub.3 H.sub.7                                                                  H  OCH.sub.3                                                                          OCH.sub.3                                              O     H  CF.sub.3                                                                            H  OCH.sub.3                                                                          OCH.sub.3                                              O     H  H     CH.sub.3                                                                         OCH.sub.3                                                                          OCH.sub.3                                              S     H  H     H  CH.sub.3                                                                           OCH.sub.3  203-206° (d)                         S     H  H     H  CH.sub.3                                                                           CH.sub.3                                               S     H  H     H  OCH.sub.3                                                                          OCH.sub.3  210-213° (d)                         S     H  H     H  Cl   OCH.sub.3  203-206° (d)                         S     H  H     H  Br   OCH.sub.3                                              S     H  H     H  F    OCH.sub.3                                              S     H  H     H  OCF.sub.2 H                                                                        OCH.sub.3                                              S     H  H     H  CF.sub.3                                                                           OCH.sub.3                                              S     H  H     H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                              S     H  H     H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                              S     H  H     H  OCF.sub.2 H                                                                        OCF.sub.2 H                                                                              202.5-205°                           S     H  H     H  CH.sub.3                                                                           OCF.sub.2 H                                            S     H  H     H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                    S     H  H     H  OCH.sub.3                                                                          SCH.sub.3                                              S(O)  H  H     H  CH.sub.3                                                                           OCH.sub.3                                              S(O)  H  H     H  CH.sub.3                                                                           CH.sub.3                                               S(O)  H  H     H  OCH.sub.3                                                                          OCH.sub.3                                              S(O)  H  H     H  Cl   OCH.sub.3                                              S(O)  H  H     H  Br   OCH.sub.3                                              S(O)  H  H     H  F    OCH.sub.3                                              S(O)  H  H     H  OCF.sub.2 H                                                                        OCH.sub.3                                              S(O)  H  H     H  CF.sub.3                                                                           OCH.sub.3                                              S(O)  H  H     H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                              S(O)  H  H     H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                              S(O)  H  H     H  OCF.sub.2 H                                                                        OCF.sub.2 H                                            S(O)  H  H     H  CH.sub.3                                                                           OCF.sub.2 H                                            S(O)  H  H     H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                    SO.sub.2                                                                            H  H     H  CH.sub.3                                                                           OCH.sub.3                                              SO.sub.2                                                                            H  H     H  CH.sub.3                                                                           CH.sub.3                                               SO.sub.2                                                                            H  H     H  OCH.sub.3                                                                          OCH.sub.3  170-173° (d)                         SO.sub.2                                                                            H  H     H  Cl   OCH.sub.3                                              SO.sub.2                                                                            H  H     H  Br   OCH.sub.3                                              SO.sub.2                                                                            H  H     H  F    OCH.sub.3                                              SO.sub.2                                                                            H  H     H  OCF.sub.2 H                                                                        OCH.sub.3                                              SO.sub.2                                                                            H  H     H  CF.sub.3                                                                           OCH.sub.3                                              SO.sub. 2                                                                           H  H     H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                              SO.sub.2                                                                            H  H     H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                              SO.sub.2                                                                            H  H     H  OCF.sub.2 H                                                                        OCF.sub.2 H                                            SO.sub.2                                                                            H  H     H  CH.sub.3                                                                           OCF.sub.2 H                                            SO.sub.2                                                                            H  H     H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                    SO.sub.2                                                                            H  H     H  OCH.sub.3                                                                          SCH.sub.3                                              NH    H  H     H  CH.sub.3                                                                           OCH.sub.3                                              NH    H  H     H  CH.sub.3                                                                           CH.sub.3                                               NH    H  H     H  OCH.sub.3                                                                          OCH.sub.3                                              NCH.sub.3                                                                           H  H     H  CH.sub.3                                                                           OCH.sub.3                                              NCH.sub.3                                                                           H  H     H  CH.sub.3                                                                           CH.sub.3                                               NCH.sub.3                                                                           H  H     H  OCH.sub.3                                                                          OCH.sub.3                                              NC.sub.2 H.sub.5                                                                    H  H     H  CH.sub.3                                                                           OCH.sub.3                                              NC.sub.2 H.sub.5                                                                    H  H     H  CH.sub.3                                                                           CH.sub.3                                               NC.sub.2 H.sub.5                                                                    H  H     H  OCH.sub.3                                                                          OCH.sub.3                                              Ni-C.sub.3 H.sub.7                                                                  H  H     H  CH.sub.3                                                                           OCH.sub.3                                              Ni-C.sub.3 H.sub.7                                                                  H  H     H  CH.sub.3                                                                           CH.sub.3                                               Ni-C.sub.3 H.sub.7                                                                  H  H     H  OCH.sub.3                                                                          OCH.sub.3                                              __________________________________________________________________________

                  TABLE Ia                                                        ______________________________________                                         ##STR14##                                                                    Q   R.sub.1                                                                              R.sub.2                                                                             R.sub.6                                                                            R.sub.7                                                                           R.sub.8                                                                            R   X     Y     m.p. (°C.)              ______________________________________                                        O   Cl     H     Cl   Cl  Cl   H   OCH.sub.3                                                                           OCH.sub.3                            O   F      H     F    F   F    H   OCH.sub.3                                                                           OCH.sub.3                            S   Cl     H     Cl   Cl  Cl   H   OCH.sub.3                                                                           OCH.sub.3                            S   F      H     F    F   F    H   OCH.sub.3                                                                           OCH.sub.3                            ______________________________________                                    

                                      TABLE II                                    __________________________________________________________________________     ##STR15##                                                                    Q     R.sub.1                                                                          R.sub.2                                                                             R  X    Y          m.p. (°C.)                           __________________________________________________________________________    O     H  H     H  CH.sub.3                                                                           OCH.sub.3  199-202° (d)                         O     H  H     H  OCH.sub.3                                                                          OCH.sub.3  202-205° (d)                         O     H  H     H  CH.sub.3                                                                           CH.sub.3                                               O     H  H     H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                              O     H  H     H  OC.sub.2 H.sub.5                                                                   CH.sub.3                                               O     H  H     H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                              O     H  H     H  OCF.sub.2 H                                                                        CH.sub.3                                               O     H  H     H  OCF.sub.2 H                                                                        OCH.sub.3                                              O     H  H     H  OCF.sub.2 H                                                                        OCF.sub.2 H                                            O     H  H     H  OCF.sub.2 H                                                                        CF.sub.3                                               O     H  H     H  CF.sub.3                                                                           CF.sub.3                                               O     H  H     H  CF.sub.3                                                                           OCH.sub.3                                              O     H  H     H  CF.sub.3                                                                           OC.sub.2 H.sub.5                                       O     H  H     H  OCH.sub.3                                                                          H                                                      O     H  H     H  OCH.sub.3                                                                          NH.sub.2                                               O     H  H     H  OCH.sub.3                                                                          NHCH.sub.3                                             O     H  H     H  OCH.sub.3                                                                          N(CH.sub.3).sub.2                                      O     H  H     H  OCH.sub.3                                                                          n-C.sub.4 H.sub.9                                      O     H  H     H  OCH.sub.3                                                                          CH.sub.2 OCH.sub.3                                     O     H  H     H  OCH.sub.3                                                                          CH.sub.2 OC.sub.2 H.sub.5                              O     H  H     H  CH.sub.3                                                                           Oi-C.sub.3 H.sub.7                                     O     H  H     H  CH.sub.3                                                                           On-C.sub.4 H.sub.9                                     O     H  H     H  CH.sub.3                                                                           OCH.sub.2 CHCH.sub.2                                   O     H  H     H  CH.sub.3                                                                           OCH.sub.2 CCH                                          O     H  H     H  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OCH.sub.3                           O     H  H     H  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 F                                   O     H  H     H  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 Cl                                  O     H  H     H  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 Br                                  O     H  H     H  CH.sub.3                                                                           CH(OCH.sub.3).sub.2                                    O     H  H     H  CH.sub.3                                                                           CH(OC.sub.2 H.sub.5 ).sub.2                            O     H  H     H  CH.sub.3                                                                           OCH.sub.2 C(CH.sub.3)CH.sub.2                          O     H  H     H  CH.sub.3                                                                           OCH.sub.2 CCCH.sub.3                                   O     H  H     H  OCH.sub.3                                                                          SCH.sub.3                                              O     H  H     H  OCH.sub.3                                                                          SC.sub.2 H.sub.5                                       O     H  H     H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                    O     H  H     H  OCH.sub.3                                                                          CH(OC.sub.2 H.sub.5).sub.2                              O    H  H     H  OCH.sub.3                                                                           ##STR16##                                              O    H  H     H  OCH.sub.3                                                                           ##STR17##                                              O    H  H     H  OCH.sub.3                                                                          CH.sub.2 Cl                                            O     H  H     H  OCH.sub.3                                                                          SCF.sub.2 H                                            O     H  H     H  CH.sub.3                                                                           OCF.sub.2 CF.sub.2 H                                   O     H  H     H  CH.sub.3                                                                           OCF.sub.2 CHCF                                         O     H  H     H  CH.sub.3                                                                           OCF.sub.2 CHBrF                                        O     H  H     H  CH.sub.3                                                                           OCF.sub.2 CHFCF.sub.3                                  O     H  H     H  CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                     O     CH.sub.3                                                                         H     H  OCH.sub.3                                                                          OCH.sub.3                                              O     H  Cl    H  CH.sub.3                                                                           OCH.sub.3                                              O     H  Br    H  CH.sub.3                                                                           OCH.sub.3                                              O     H  OCH.sub.3                                                                           H  OCH.sub.3                                                                          OCH.sub.3                                              O     H  OC.sub.2 H.sub.5                                                                    H  OCH.sub.3                                                                          OCH.sub.3                                              O     H  On-C.sub.3 H.sub.7                                                                  H  OCH.sub.3                                                                          OCH.sub.3                                              O     H  CF.sub.3                                                                            H  OCH.sub.3                                                                          OCH.sub.3                                              O     H  H     CH.sub.3                                                                         OCH.sub.3                                                                          OCH.sub.3                                              S     H  H     H  CH.sub.3                                                                           OCH.sub.3  180.5-185° (d)                       S     H  H     H  CH.sub.3                                                                           CH.sub.3                                               S     H  H     H  OCH.sub.3                                                                          OCH.sub.3  190-194° (d)                         S     H  H     H  OCF.sub.2 H                                                                        OCH.sub.3                                              S     H  H     H  CF.sub.3                                                                           OCH.sub.3                                              S     H  H     H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                              S     H  H     H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                              S     H  H     H  OCF.sub.2 H                                                                        OCF.sub.2 H                                            S     H  H     H  CH.sub.3                                                                           OCF.sub.2 H                                            S     H  H     H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                    S     H  H     H  OCH.sub.3                                                                          SCH.sub.3                                              S(O)  H  H     H  CH.sub.3                                                                           OCH.sub.3                                              S(O)  H  H     H  CH.sub.3                                                                           CH.sub.3                                               S(O)  H  H     H  OCH.sub.3                                                                          OCH.sub.3                                              S(O)  H  H     H  OCF.sub. 2 H                                                                       OCH.sub.3                                              S(O)  H  H     H  CF.sub.3                                                                           OCH.sub.3                                              S(O)  H  H     H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                              S(O)  H  H     H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                              S(O)  H  H     H  OCF.sub.2 H                                                                        OCF.sub.2 H                                            S(O)  H  H     H  CH.sub.3                                                                           OCF.sub.2 H                                            S(O)  H  H     H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                    SO.sub.2                                                                            H  H     H  CH.sub.3                                                                           OCH.sub.3  183-186° (d)                         SO.sub.2                                                                            H  H     H  CH.sub.3                                                                           CH.sub.3                                               SO.sub.2                                                                            H  H     H  OCH.sub.3                                                                          OCH.sub.3                                              SO.sub.2                                                                            H  H     H  OCF.sub.2 H                                                                        OCH.sub.3                                              SO.sub.2                                                                            H  H     H  CF.sub.3                                                                           OCH.sub.3                                              SO.sub.2                                                                            H  H     H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                              SO.sub.2                                                                            H  H     H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                              SO.sub.2                                                                            H  H     H  OCF.sub.2 H                                                                        OCF.sub.2 H                                            SO.sub.2                                                                            H  H     H  CH.sub.3                                                                           OCF.sub.2 H                                            SO.sub.2                                                                            H  H     H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                    SO.sub.2                                                                            H  H     H  OCH.sub.3                                                                          SCH.sub.3                                              NH    H  H     H  CH.sub.3                                                                           OCH.sub.3                                              NH    H  H     H  CH.sub.3                                                                           CH.sub.3                                               NH    H  H     H  OCH.sub.3                                                                          OCH.sub.3                                              NCH.sub.3                                                                           H  H     H  CH.sub.3                                                                           OCH.sub.3                                              NCH.sub.3                                                                           H  H     H  CH.sub.3                                                                           CH.sub.3                                               NCH.sub.3                                                                           H  H     H  OCH.sub.3                                                                          OCH.sub.3                                              NC.sub.2 H.sub.5                                                                    H  H     H  CH.sub.3                                                                           OCH.sub.3                                              NC.sub.2 H.sub.5                                                                    H  H     H  CH.sub.3                                                                           CH.sub.3                                               NC.sub.2 H.sub.5                                                                    H  H     H  OCH.sub.3                                                                          OCH.sub.3                                              Ni-C.sub.3 H.sub.7                                                                  H  H     H  CH.sub.3                                                                           OCH.sub.3                                              Ni-C.sub.3 H.sub.7                                                                  H  H     H  CH.sub.3                                                                           CH.sub.3                                               Ni-C.sub.3 H.sub.7                                                                  H  H     H  OCH.sub.3                                                                          OCH.sub.3                                              __________________________________________________________________________

                  TABLE IIa                                                       ______________________________________                                         ##STR18##                                                                    Q   R.sub.1                                                                              R.sub.2                                                                             R.sub.6                                                                            R.sub.7                                                                           R.sub.8                                                                            R   X     Y     m.p. (°C.)              ______________________________________                                        O   Cl     H     Cl   Cl  Cl   H   OCH.sub.3                                                                           OCH.sub.3                            O   F      H     F    F   F    H   OCH.sub.3                                                                           OCH.sub.3                            S   Cl     H     Cl   Cl  Cl   H   OCH.sub.3                                                                           OCH.sub.3                            S   F      H     F    F   F    H   OCH.sub.3                                                                           OCH.sub.3                            ______________________________________                                    

                                      TABLE III                                   __________________________________________________________________________     ##STR19##                                                                    Q     R.sub.1                                                                          R.sub.2                                                                             R.sub.4                                                                          R.sub.5                                                                          R  X    Y          m.p. (°C.)                     __________________________________________________________________________    O     H  H     H  H  H  CH.sub.3                                                                           OCH.sub.3                                        O     H  H     H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        O     H  H     H  H  H  CH.sub.3                                                                           CH.sub.3                                         O     H  H     H  H  H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                        O     H  H     H  H  H  OC.sub.2 H.sub.5                                                                   CH.sub.3                                         O     H  H     H  H  H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                        O     H  H     H  H  H  Cl   OCH.sub.3                                        O     H  H     H  H  H  Br   OCH.sub.3                                        O     H  H     H  H  H  F    OCH.sub.3                                        O     H  H     H  H  H  OCF.sub.2 H                                                                        CH.sub.3                                         O     H  H     H  H  H  OCF.sub.2 H                                                                        OCH.sub.3                                        O     H  H     H  H  H  OCF.sub.2 H                                                                        OCF.sub.2 H                                      O     H  H     H  H  H  OCF.sub.2 H                                                                        CF.sub.3                                         O     H  H     H  H  H  CF.sub.3                                                                           CF.sub.3                                         O     H  H     H  H  H  CF.sub.3                                                                           OCH.sub.3                                        O     H  H     H  H  H  CF.sub.3                                                                           OC.sub.2 H.sub.5                                 O     H  H     H  H  H  OCH.sub.3                                                                          H                                                O     H  H     H  H  H  OCH.sub.3                                                                          NH.sub.2                                         O     H  H     H  H  H  OCH.sub.3                                                                          NHCH.sub.3                                       O     H  H     H  H  H  OCH.sub.3                                                                          N(CH.sub.3).sub.2                                O     H  H     H  H  H  OCH.sub.3                                                                          n-C.sub.4 H.sub.9                                O     H  H     H  H  H  OCH.sub.3                                                                          CH.sub.2 OCH.sub.3                               O     H  H     H  H  H  OCH.sub.3                                                                          CH.sub.2 OC.sub.2 H.sub.5                        O     H  H     H  H  H  CH.sub.3                                                                           Oi-C.sub.3 H.sub.7                               O     H  H     H  H  H  CH.sub.3                                                                           On-C.sub.4 H.sub.9                               O     H  H     H  H  H  CH.sub.3                                                                           OCH.sub.2 CHCH.sub.2                             O     H  H     H  H  H  CH.sub.3                                                                           OCH.sub.2 CCH                                    O     H  H     H  H  H  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OCH.sub.3                     O     H  H     H  H  H  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 F                             O     H  H     H  H  H  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 Cl                            O     H  H     H  H  H  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 Br                            O     H  H     H  H  H  CH.sub.3                                                                           CH(OCH.sub.3).sub.2                              O     H  H     H  H  H  CH.sub.3                                                                           CH(OC.sub.2 H.sub.5).sub.2                       O     H  H     H  H  H  CH.sub.3                                                                           OCH.sub.2 C(CH.sub.3)CH.sub.2                    O     H  H     H  H  H  CH.sub.3                                                                           OCH.sub.2 CCCH.sub.3                             O     H  H     H  H  H  OCH.sub.3                                                                          SCH.sub.3                                        O     H  H     H  H  H  OCH.sub.3                                                                          SC.sub.2 H.sub.5                                 O     H  H     H  H  H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                              O     H  H     H  H  H  OCH.sub.3                                                                          CH(OC.sub.2 H.sub.5).sub.2                        O    H  H     H  H  H  OCH.sub.3                                                                           ##STR20##                                        O    H  H     H  H  H  OCH.sub.3                                                                           ##STR21##                                        O    H  H     H  H  H  OCH.sub.3                                                                          CH.sub.2 Cl                                      O     H  H     H  H  H  OCH.sub.3                                                                          SCF.sub.2 H                                      O     H  H     H  H  H  CH.sub.3                                                                           OCF.sub.2 CF.sub.2 H                             O     H  H     H  H  H  CH.sub.3                                                                           OCF.sub.2 CHCF                                   O     H  H     H  H  H  CH.sub.3                                                                           OCF.sub.2 CHBrF                                  O     H  H     H  H  H  CH.sub.3                                                                           OCF.sub.2 CHFCF.sub.3                            O     H  H     H  H  H  CH.sub.3                                                                           OCH.sub.2 CF.sub.3                               O     CH.sub.3                                                                         H     H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        O     H  Cl    H  H  H  CH.sub.3                                                                           OCH.sub.3                                        O     H  Br    H  H  H  CH.sub.3                                                                           OCH.sub.3                                        O     H  OCH.sub.3                                                                           H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        O     H  OC.sub.2 H.sub.5                                                                    H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        O     H  On-C.sub.3 H.sub.7                                                                  H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        O     H  CF.sub.3                                                                            H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        O     H  H     H  H  CH.sub.3                                                                         OCH.sub.3                                                                          OCH.sub.3                                        S     H  H     H  H  H  CH.sub.3                                                                           OCH.sub.3                                        S     H  H     H  H  H  CH.sub.3                                                                           CH.sub.3                                         S     H  H     H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        S     H  H     H  H  H  Cl   OCH.sub.3                                        S     H  H     H  H  H  Br   OCH.sub.3                                        S     H  H     H  H  H  F    OCH.sub.3                                        S     H  H     H  H  H  OCF.sub.2 H                                                                        OCH.sub.3                                        S     H  H     H  H  H  CF.sub.3                                                                           OCH.sub.3                                        S     H  H     H  H  H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                        S     H  H     H  H  H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                        S     H  H     H  H  H  OCF.sub.2 H                                                                        OCF.sub.2 H                                      S     H  H     H  H  H  CH.sub.3                                                                           OCF.sub.2 H                                      S     H  H     H  H  H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                              S     H  H     H  H  H  OCH.sub.3                                                                          SCH.sub.3                                        S(O)  H  H     H  H  H  CH.sub.3                                                                           OCH.sub.3                                        S(O)  H  H     H  H  H  CH.sub.3                                                                           CH.sub.3                                         S(O)  H  H     H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        S(O)  H  H     H  H  H  Cl   OCH.sub.3                                        S(O)  H  H     H  H  H  Br   OCH.sub.3                                        S(O)  H  H     H  H  H  OCF.sub.2 H                                                                        OCH.sub. 3                                       S(O)  H  H     H  H  H  CF.sub.3                                                                           OCH.sub.3                                        S(O)  H  H     H  H  H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                        S(O)  H  H     H  H  H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                        S(O)  H  H     H  H  H  OCF.sub.2 H                                                                        OCF.sub.2 H                                      S(O)  H  H     H  H  H  CH.sub.3                                                                           OCF.sub.2 H                                      S(O)  H  H     H  H  H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                              S(0)  H  H     H  H  H  F    OCH.sub.3                                        SO.sub.2                                                                            H  H     H  H  H  CH.sub.3                                                                           OCH.sub.3                                        SO.sub.2                                                                            H  H     H  H  H  CH.sub.3                                                                           CH.sub.3                                         SO.sub.2                                                                            H  H     H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        SO.sub.2                                                                            H  H     H  H  H  Cl   OCH.sub.3                                        SO.sub.2                                                                            H  H     H  H  H  F    OCH.sub.3                                        SO.sub.2                                                                            H  H     H  H  H  Br   OCH.sub.3                                        SO.sub.2                                                                            H  H     H  H  H  OCF.sub.2 H                                                                        OCH.sub.3                                        SO.sub.2                                                                            H  H     H  H  H  CF.sub.3                                                                           OCH.sub.3                                        SO.sub.2                                                                            H  H     H  H  H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                        SO.sub.2                                                                            H  H     H  H  H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                        SO.sub.2                                                                            H  H     H  H  H  OCF.sub.2 H                                                                        OCF.sub.2 H                                      SO.sub.2                                                                            H  H     H  H  H  CH.sub.3                                                                           OCF.sub.2 H                                      SO.sub.2                                                                            H  H     H  H  H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                              SO.sub.2                                                                            H  H     H  H  H  OCH.sub.3                                                                          SCH.sub.3                                        NH    H  H     H  H  H  CH.sub.3                                                                           OCH.sub.3                                        NH    H  H     H  H  H  CH.sub.3                                                                           CH.sub.3                                         NH    H  H     H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        NCH.sub.3                                                                           H  H     H  H  H  CH.sub.3                                                                           OCH.sub.3                                        NCH.sub.3                                                                           H  H     H  H  H  CH.sub.3                                                                           CH.sub.3                                         NCH.sub.3                                                                           H  H     H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        NC.sub.2 H.sub.5                                                                    H  H     H  H  H  CH.sub.3                                                                           OCH.sub.3                                        NC.sub.2 H.sub.5                                                                    H  H     H  H  H  CH.sub.3                                                                           CH.sub.3                                         NC.sub.2 H.sub.5                                                                    H  H     H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        Ni-C.sub.3 H.sub.7                                                                  H  H     H  H  H  CH.sub.3                                                                           OCH.sub.3                                        Ni-C.sub.3 H.sub.7                                                                  H  H     H  H  H  CH.sub.3                                                                           CH.sub.3                                         Ni-C.sub.3 H.sub.7                                                                  H  H     H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        O     H  H     CH.sub.3                                                                         H  H  CH.sub.3                                                                           OCH.sub.3                                        O     H  H     CH.sub.3                                                                         H  H  OCH.sub.3                                                                          OCH.sub.3                                        O     H  H     CH.sub.3                                                                         H  H  CH.sub.3                                                                           CH.sub.3                                         O     H  H     CH.sub.3                                                                         CH.sub.3                                                                         H  CH.sub.3                                                                           OCH.sub.3                                        O     H  H     CH.sub.3                                                                         CH.sub.3                                                                         H  OCH.sub.3                                                                          OCH.sub.3                                        O     H  H     CH.sub.3                                                                         CH.sub.3                                                                         H  CH.sub.3                                                                           CH.sub.3                                         __________________________________________________________________________

                                      TABLE IV                                    __________________________________________________________________________     ##STR22##                                                                    Q     R.sub.1                                                                          R.sub.2                                                                             R.sub.4                                                                          R.sub.5                                                                          R  X    Y          m.p. (°C.)                     __________________________________________________________________________    O     H  H     H  H  H  CH.sub.3                                                                           OCH.sub.3                                        O     H  H     H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        O     H  H     H  H  H  CH.sub.3                                                                           CH.sub.3                                         O     H  H     H  H  H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                        O     H  H     H  H  H  OC.sub.2 H.sub.5                                                                   CH.sub.3                                         O     H  H     H  H  H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                        O     H  H     H  H  H  OCF.sub.2 H                                                                        CH.sub.3                                         O     H  H     H  H  H  OCF.sub.2 H                                                                        OCH.sub.3                                        O     H  H     H  H  H  OCF.sub.2 H                                                                        OCF.sub.2 H                                      O     H  H     H  H  H  OCF.sub.2 H                                                                        CF.sub.3                                         O     H  H     H  H  H  CF.sub.3                                                                           CF.sub.3                                         O     H  H     H  H  H  CF.sub.3                                                                           OCH.sub.3                                        O     H  H     H  H  H  CF.sub.3                                                                           OC.sub.2 H.sub.5                                 O     H  H     H  H  H  OCH.sub.3                                                                          H                                                O     H  H     H  H  H  OCH.sub.3                                                                          NH.sub.2                                         O     H  H     H  H  H  OCH.sub.3                                                                          NHCH.sub.3                                       O     H  H     H  H  H  OCH.sub.3                                                                          N(CH.sub.3 ).sub.2                               O     H  H     H  H  H  OCH.sub.3                                                                          n-C.sub.4 H.sub.9                                O     H  H     H  H  H  OCH.sub.3                                                                          CH.sub.2 OCH.sub.3                               O     H  H     H  H  H  OCH.sub.3                                                                          CH.sub.2 OC.sub.2 H.sub.5                        O     H  H     H  H  H  CH.sub.3                                                                           Oi-C.sub.3 H.sub.7                               O     H  H     H  H  H  CH.sub.3                                                                           On-C.sub.4 H.sub.9                               O     H  H     H  H  H  CH.sub.3                                                                           OCH.sub.2 CHCH.sub.2                             O     H  H     H  H  H  CH.sub.3                                                                           OCH.sub.2 CCH                                    O     H  H     H  H  H  CH.sub. 3                                                                          OCH.sub.2 CH.sub.2 OCH.sub.3                     O     H  H     H  H  H  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 F                             O     H  H     H  H  H  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 Cl                            O     H  H     H  H  H  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 Br                            O     H  H     H  H  H  CH.sub.3                                                                           CH(OCH.sub.3).sub.2                              O     H  H     H  H  H  CH.sub.3                                                                           CH(OC.sub.2 H.sub.5).sub.2                       O     H  H     H  H  H  CH.sub.3                                                                           OCH.sub.2 C(CH.sub.3)CH.sub.2                    O     H  H     H  H  H  CH.sub.3                                                                           OCH.sub.2 CCCH.sub.3                             O     H  H     H  H  H  OCH.sub.3                                                                          SCH.sub.3                                        O     H  H     H  H  H  OCH.sub.3                                                                          SC.sub.2 H.sub.5                                 O     H  H     H  H  H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                              O     H  H     H  H  H  OCH.sub.3                                                                          CH(OC.sub.2 H.sub.5 ).sub.2                       O    H  H     H  H  H  OCH.sub.3                                                                           ##STR23##                                        O    H  H     H  H  H  OCH.sub.3                                                                           ##STR24##                                        O    H  H     H  H  H  OCH.sub.3                                                                          CH.sub.2 Cl                                      O     H  H     H  H  H  OCH.sub.3                                                                          SCF.sub.2 H                                      O     H  H     H  H  H  CH.sub.3                                                                           OCF.sub.2 CF.sub.2 H                             O     H  H     H  H  H  CH.sub.3                                                                           OCF.sub.2 CHCF                                   O     H  H     H  H  H  CH.sub.3                                                                           OCF.sub.2 CHBrF                                  O     H  H     H  H  H  CH.sub.3                                                                           OCF.sub.2 CHFCF.sub.3                            O     H  H     H  H  H  CH.sub.3                                                                           OCH.sub.2 CF.sub.3                               O     CH.sub.3                                                                         H     H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        O     H  Cl    H  H  H  CH.sub.3                                                                           OCH.sub.3                                        O     H  Br    H  H  H  CH.sub.3                                                                           OCH.sub.3                                        O     H  OCH.sub.3                                                                           H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        O     H  OC.sub.2 H.sub.5                                                                    H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        O     H  On-C.sub.3 H.sub.7                                                                  H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        O     H  CF.sub.3                                                                            H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        O     H  H     H  H  CH.sub.3                                                                         OCH.sub.3                                                                          OCH.sub.3                                        S     H  H     H  H  H  CH.sub.3                                                                           OCH.sub.3                                        S     H  H     H  H  H  CH.sub.3                                                                           CH.sub.3                                         S     H  H     H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        S     H  H     H  H  H  OCF.sub.2 H                                                                        OCH.sub.3                                        S     H  H     H  H  H  CF.sub.3                                                                           OCH.sub.3                                        S     H  H     H  H  H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                        S     H  H     H  H  H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                        S     H  H     H  H  H  OCF.sub.2 H                                                                        OCF.sub.2 H                                      S     H  H     H  H  H  CH.sub.3                                                                           OCF.sub.2 H                                      S     H  H     H  H  H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                              S     H  H     H  H  H  OCH.sub.3                                                                          SCH.sub.3                                        S(O)  H  H     H  H  H  CH.sub.3                                                                           OCH.sub.3                                        S(O)  H  H     H  H  H  CH.sub.3                                                                           CH.sub.3                                         S(O)  H  H     H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        S(O)  H  H     H  H  H  OCF.sub.2 H                                                                        OCH.sub.3                                        S(O)  H  H     H  H  H  CF.sub.3                                                                           OCH.sub.3                                        S(O)  H  H     H  H  H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                        S(O)  H  H     H  H  H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                        S(O)  H  H     H  H  H  OCF.sub.2 H                                                                        OCF.sub.2 H                                      S(O)  H  H     H  H  H  CH.sub.3                                                                           OCF.sub.2 H                                      S(O)  H  H     H  H  H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                              SO.sub.2                                                                            H  H     H  H  H  CH.sub.3                                                                           OCH.sub.3                                        SO.sub.2                                                                            H  H     H  H  H  CH.sub.3                                                                           CH.sub.3                                         SO.sub.2                                                                            H  H     H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        SO.sub.2                                                                            H  H     H  H  H  OCF.sub.2 H                                                                        OCH.sub.3                                        SO.sub.2                                                                            H  H     H  H  H  CF.sub.3                                                                           OCH.sub.3                                        SO.sub.2                                                                            H  H     H  H  H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                        SO.sub.2                                                                            H  H     H  H  H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                        SO.sub.2                                                                            H  H     H  H  H  OCF.sub.2 H                                                                        OCF.sub.2 H                                      SO.sub.2                                                                            H  H     H  H  H  CH.sub.3                                                                           OCF.sub.2 H                                      SO.sub.2                                                                            H  H     H  H  H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                              SO.sub.2                                                                            H  H     H  H  H  OCH.sub.3                                                                          SCH.sub.3                                        NH    H  H     H  H  H  CH.sub.3                                                                           OCH.sub.3                                        NH    H  H     H  H  H  CH.sub.3                                                                           CH.sub.3                                         NH    H  H     H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        NCH.sub.3                                                                           H  H     H  H  H  CH.sub.3                                                                           OCH.sub.3                                        NCH.sub.3                                                                           H  H     H  H  H  CH.sub.3                                                                           CH.sub.3                                         NCH.sub.3                                                                           H  H     H  H  H  OCH.sub. 3                                                                         OCH.sub.3                                        NC.sub.2 H.sub.5                                                                    H  H     H  H  H  CH.sub.3                                                                           OCH.sub.3                                        NC.sub.2 H.sub.5                                                                    H  H     H  H  H  CH.sub.3                                                                           CH.sub.3                                         NC.sub.2 H.sub.5                                                                    H  H     H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        Ni-C.sub.3 H.sub.7                                                                  H  H     H  H  H  CH.sub.3                                                                           OCH.sub.3                                        Ni-C.sub.3 H.sub.7                                                                  H  H     H  H  H  CH.sub.3                                                                           CH.sub.3                                         Ni-C.sub.3 H.sub.7                                                                  H  H     H  H  H  OCH.sub.3                                                                          OCH.sub.3                                        O     H  H     CH.sub.3                                                                         H  H  OCH.sub.3                                                                          CH.sub.3                                         O     H  H     CH.sub.3                                                                         H  H  OCH.sub.3                                                                          OCH.sub.3                                        O     H  H     CH.sub.3                                                                         H  H  CH.sub.3                                                                           CH.sub.3                                         O     H  H     CH.sub.3                                                                         CH.sub.3                                                                         H  OCH.sub.3                                                                          CH.sub.3                                         O     H  H     CH.sub.3                                                                         CH.sub.3                                                                         H  OCH.sub.3                                                                          OCH.sub.3                                        O     H  H     CH.sub.3                                                                         CH.sub.3                                                                         H  CH.sub.3                                                                           CH.sub.3                                         __________________________________________________________________________

                                      TABLE V                                     __________________________________________________________________________     ##STR25##                                                                    Q     R.sub.1                                                                          R.sub.2                                                                             R.sub.4                                                                          R  X    Y          m.p. (°C.)                        __________________________________________________________________________    O     H  H     H  H  CH.sub.3                                                                           OCH.sub.3                                           O     H  H     H  H  OCH.sub.3                                                                          OCH.sub.3                                           O     H  H     H  H  CH.sub.3                                                                           CH.sub.3                                            O     H  H     H  H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                           O     H  H     H  H  OC.sub.2 H.sub.5                                                                   CH.sub.3                                            O     H  H     H  H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                           O     H  H     H  H  Cl   OCH.sub.3                                           O     H  H     H  H  Br   OCH.sub.3                                           O     H  H     H  H  F    OCH.sub.3                                           O     H  H     H  H  OCF.sub.2 H                                                                        CH.sub.3                                            O     H  H     H  H  OCF.sub.2 H                                                                        OCH.sub.3                                           O     H  H     H  H  OCF.sub.2 H                                                                        OCF.sub.2 H                                         O     H  H     H  H  OCF.sub.2 H                                                                        CF.sub.3                                            O     H  H     H  H  CF.sub.3                                                                           CF.sub.3                                            O     H  H     H  H  CF.sub.3                                                                           OCH.sub.3                                           O     H  H     H  H  CF.sub.3                                                                           OC.sub.2 H.sub.5                                    O     H  H     H  H  OCH.sub.3                                                                          H                                                   O     H  H     H  H  OCH.sub.3                                                                          NH.sub.2                                            O     H  H     H  H  OCH.sub.3                                                                          NHCH.sub.3                                          O     H  H     H  H  OCH.sub.3                                                                          N(CH.sub.3).sub.2                                   O     H  H     H  H  OCH.sub.3                                                                          n-C.sub.4 H.sub.9                                   O     H  H     H  H  OCH.sub.3                                                                          CH.sub.2 OCH.sub.3                                  O     H  H     H  H  OCH.sub.3                                                                          CH.sub.2 OC.sub.2 H.sub.5                           O     H  H     H  H  CH.sub.3                                                                           Oi-C.sub.3 H.sub.7                                  O     H  H     H  H  CH.sub.3                                                                           On-C.sub.4 H.sub.9                                  O     H  H     H  H  CH.sub.3                                                                           OCH.sub.2 CHCH.sub.2                                O     H  H     H  H  CH.sub.3                                                                           OCH.sub.2 CCH                                       O     H  H     H  H  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OCH.sub.3                        O     H  H     H  H  CH.sub.3                                                                           OCH.sub.2 CH.sub. 2 F                               O     H  H     H  H  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 Cl                               O     H  H     H  H  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 Br                               O     H  H     H  H  CH.sub.3                                                                           CH(OCH.sub.3).sub.2                                 O     H  H     H  H  CH.sub.3                                                                           CH(OC.sub.2 H.sub.5).sub.2                          O     H  H     H  H  CH.sub.3                                                                           OCH.sub.2 C(CH.sub.3)CH.sub.2                       O     H  H     H  H  CH.sub.3                                                                           OCH.sub.2 CCCH.sub.3                                O     H  H     H  H  OCH.sub.3                                                                          SCH.sub.3                                           O     H  H     H  H  OCH.sub.3                                                                          SC.sub.2 H.sub.5                                    O     H  H     H  H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                 O     H  H     H  H  OCH.sub.3                                                                          CH(OC.sub.2 H.sub.5).sub.2                           O    H  H     H  H  OCH.sub.3                                                                           ##STR26##                                           O    H  H     H  H  OCH.sub.3                                                                           ##STR27##                                           O    H  H     H  H  OCH.sub.3                                                                          CH.sub.2 Cl                                         O     H  H     H  H  OCH.sub.3                                                                          SCF.sub.2 H                                         O     H  H     H  H  CH.sub.3                                                                           OCF.sub.2 CF.sub.2 H                                O     H  H     H  H  CH.sub.3                                                                           OCF.sub.2 CHCF                                      O     H  H     H  H  CH.sub.3                                                                           OCF.sub.2 CHBrF                                     O     H  H     H  H  CH.sub.3                                                                           OCF.sub.2 CHFCF.sub.3                               O     H  H     H  H  CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                  O     CH.sub.3                                                                         H     H  H  OCH.sub.3                                                                          OCH.sub.3                                           O     H  Cl    H  H  CH.sub.3                                                                           OCH.sub.3                                           O     H  Br    H  H  CH.sub.3                                                                           OCH.sub.3                                           O     H  OCH.sub.3                                                                           H  H  OCH.sub.3                                                                          OCH.sub.3                                           O     H  OC.sub.2 H.sub.5                                                                    H  H  OCH.sub.3                                                                          OCH.sub.3                                           O     H  On-C.sub.3 H.sub.7                                                                  H  H  OCH.sub.3                                                                          OCH.sub.3                                           O     H  CF.sub.3                                                                            H  H  OCH.sub.3                                                                          OCH.sub.3                                           O     H  H     H  CH.sub.3                                                                         OCH.sub.3                                                                          OCH.sub.3                                           S     H  H     H  H  CH.sub.3                                                                           OCH.sub.3                                           S     H  H     H  H  CH.sub.3                                                                           CH.sub.3                                            S     H  H     H  H  OCH.sub.3                                                                          OCH.sub.3                                           S     H  H     H  H  Cl   OCH.sub.3                                           S     H  H     H  H  Br   OCH.sub.3                                           S     H  H     H  H  F    OCH.sub.3                                           S     H  H     H  H  OCF.sub.2 H                                                                        OCH.sub.3                                           S     H  H     H  H  CF.sub.3                                                                           OCH.sub.3                                           S     H  H     H  H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                           S     H  H     H  H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                           S     H  H     H  H  OCF.sub.2 H                                                                        OCF.sub.2 H                                         S     H  H     H  H  CH.sub.3                                                                           OCF.sub.2 H                                         S     H  H     H  H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                 S     H  H     H  H  OCH.sub.3                                                                          SCH.sub.3                                           S(O)  H  H     H  H  CH.sub.3                                                                           OCH.sub.3                                           S(O)  H  H     H  H  CH.sub.3                                                                           CH.sub.3                                            S(O)  H  H     H  H  OCH.sub.3                                                                          OCH.sub.3                                           S(O)  H  H     H  H  Cl   OCH.sub.3                                           S(O)  H  H     H  H  Br   OCH.sub.3                                           S(O)  H  H     H  H  F    OCH.sub.3                                           S(O)  H  H     H  H  OCF.sub.2 H                                                                        OCH.sub.3                                           S(O)  H  H     H  H  CF.sub.3                                                                           OCH.sub.3                                           S(O)  H  H     H  H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                           S(O)  H  H     H  H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                           S(O)  H  H     H  H  OCF.sub.2 H                                                                        OCF.sub.2 H                                         S(O)  H  H     H  H  CH.sub.3                                                                           OCF.sub.2 H                                         S(O)  H  H     H  H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                 SO.sub.2                                                                            H  H     H  H  CH.sub.3                                                                           OCH.sub. 3                                          SO.sub.2                                                                            H  H     H  H  CH.sub.3                                                                           CH.sub.3                                            SO.sub.2                                                                            H  H     H  H  OCH.sub.3                                                                          OCH.sub.3                                           SO.sub.2                                                                            H  H     H  H  Cl   OCH.sub.3                                           SO.sub.2                                                                            H  H     H  H  F    OCH.sub.3                                           SO.sub.2                                                                            H  H     H  H  Br   OCH.sub.3                                           SO.sub.2                                                                            H  H     H  H  OCF.sub.2 H                                                                        OCH.sub.3                                           SO.sub.2                                                                            H  H     H  H  CF.sub.3                                                                           OCH.sub.3                                           SO.sub.2                                                                            H  H     H  H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                           SO.sub.2                                                                            H  H     H  H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                           SO.sub.2                                                                            H  H     H  H  OCF.sub.2 H                                                                        OCF.sub.2 H                                         SO.sub.2                                                                            H  H     H  H  CH.sub.3                                                                           OCF.sub.2 H                                         SO.sub.2                                                                            H  H     H  H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                 SO.sub.2                                                                            H  H     H  H  OCH.sub.3                                                                          SCH.sub.3                                           NH    H  H     H  H  CH.sub.3                                                                           OCH.sub.3                                           NH    H  H     H  H  CH.sub.3                                                                           CH.sub.3                                            NH    H  H     H  H  OCH.sub.3                                                                          OCH.sub.3                                           NCH.sub.3                                                                           H  H     H  H  CH.sub.3                                                                           OCH.sub.3                                           NCH.sub.3                                                                           H  H     H  H  CH.sub.3                                                                           CH.sub.3                                            NCH.sub.3                                                                           H  H     H  H  OCH.sub.3                                                                          OCH.sub.3                                           NC.sub.2 H.sub.5                                                                    H  H     H  H  CH.sub.3                                                                           OCH.sub.3                                           NC.sub.2 H.sub.5                                                                    H  H     H  H  CH.sub.3                                                                           CH.sub.3                                            NC.sub.2 H.sub.5                                                                    H  H     H  H  OCH.sub.3                                                                          OCH.sub.3                                           Ni-C.sub.3 H.sub.7                                                                  H  H     H  H  CH.sub.3                                                                           OCH.sub.3                                           Ni-C.sub.3 H.sub.7                                                                  H  H     H  H  CH.sub.3                                                                           CH.sub.3                                            Ni-C.sub.3 H.sub.7                                                                  H  H     H  H  OCH.sub.3                                                                          OCH.sub.3                                           O     H  H     CH.sub.3                                                                         H  OCH.sub.3                                                                          CH.sub.3                                            O     H  H     CH.sub.3                                                                         H  OCH.sub.3                                                                          OCH.sub.3                                           O     H  H     CH.sub.3                                                                         H  CH.sub.3                                                                           CH.sub.3                                            __________________________________________________________________________

                                      TABLE VI                                    __________________________________________________________________________     ##STR28##                                                                    Q     R.sub.1                                                                          R.sub.2                                                                             R.sub.4                                                                          R  X    Y          m.p. (°C.)                        __________________________________________________________________________    O     H  H     H  H  CH.sub.3                                                                           OCH.sub.3                                           O     H  H     H  H  OCH.sub.3                                                                          OCH.sub.3                                           O     H  H     H  H  CH.sub.3                                                                           CH.sub.3                                            O     H  H     H  H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                           O     H  H     H  H  OC.sub.2 H.sub.5                                                                   CH.sub.3                                            O     H  H     H  H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                           O     H  H     H  H  OCF.sub.2 H                                                                        CH.sub.3                                            O     H  H     H  H  OCF.sub.2 H                                                                        OCH.sub.3                                           O     H  H     H  H  OCF.sub.2 H                                                                        OCF.sub.2 H                                         O     H  H     H  H  OCF.sub. 2 H                                                                       CF.sub.3                                            O     H  H     H  H  CF.sub.3                                                                           CF.sub.3                                            O     H  H     H  H  CF.sub.3                                                                           OCH.sub.3                                           O     H  H     H  H  CF.sub.3                                                                           OC.sub.2 H.sub.5                                    O     H  H     H  H  OCH.sub.3                                                                          H                                                   O     H  H     H  H  OCH.sub.3                                                                          NH.sub.2                                            O     H  H     H  H  OCH.sub.3                                                                          NHCH.sub.3                                          O     H  H     H  H  OCH.sub.3                                                                          N(CH.sub.3).sub.2                                   O     H  H     H  H  OCH.sub.3                                                                          n-C.sub.4 H.sub.9                                   O     H  H     H  H  OCH.sub.3                                                                          CH.sub.2 OCH.sub.3                                  O     H  H     H  H  OCH.sub.3                                                                          CH.sub.2 OC.sub.2 H.sub.5                           O     H  H     H  H  CH.sub.3                                                                           Oi-C.sub.3 H.sub.7                                  O     H  H     H  H  CH.sub.3                                                                           On-C.sub.4 H.sub.9                                  O     H  H     H  H  CH.sub.3                                                                           OCH.sub.2 CHCH.sub.2                                O     H  H     H  H  CH.sub.3                                                                           OCH.sub.2 CCH                                       O     H  H     H  H  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 OCH.sub.3                        O     H  H     H  H  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 F                                O     H  H     H  H  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 Cl                               O     H  H     H  H  CH.sub.3                                                                           OCH.sub.2 CH.sub.2 Br                               O     H  H     H  H  CH.sub.3                                                                           CH(OCH.sub.3).sub.2                                 O     H  H     H  H  CH.sub.3                                                                           CH(OC.sub.2 H.sub.5).sub.2                          O     H  H     H  H  CH.sub.3                                                                           OCH.sub.2 C(CH.sub.3)CH.sub.2                       O     H  H     H  H  CH.sub.3                                                                           OCH.sub.2 CCCH.sub.3                                O     H  H     H  H  OCH.sub.3                                                                          SCH.sub.3                                           O     H  H     H  H  OCH.sub.3                                                                          SC.sub.2 H.sub.5                                    O     H  H     H  H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                 O     H  H     H  H  OCH.sub.3                                                                          CH(OC.sub.2 H.sub.5).sub.2                           O    H  H     H  H  OCH.sub.3                                                                           ##STR29##                                           O    H  H     H  H  OCH.sub.3                                                                           ##STR30##                                           O    H  H     H  H  OCH.sub.3                                                                          CH.sub.2 Cl                                         O     H  H     H  H  OCH.sub.3                                                                          SCF.sub.2 H                                         O     H  H     H  H  CH.sub.3                                                                           OCF.sub.2 CF.sub.2 H                                O     H  H     H  H  CH.sub.3                                                                           OCF.sub.2 CHCF                                      O     H  H     H  H  CH.sub.3                                                                           OCF.sub.2 CHBrF                                     O     H  H     H  H  CH.sub.3                                                                           OCF.sub.2 CHFCF.sub.3                               O     H  H     H  H  CH.sub.3                                                                           OCH.sub.2 CF.sub.3                                  O     CH.sub.3                                                                         H     H  H  OCH.sub.3                                                                          OCH.sub.3                                           O     H  Cl    H  H  CH.sub.3                                                                           OCH.sub.3                                           O     H  Br    H  H  CH.sub.3                                                                           OCH.sub.3                                           O     H  OCH.sub.3                                                                           H  H  OCH.sub.3                                                                          OCH.sub.3                                           O     H  OC.sub.2 H.sub.5                                                                    H  H  OCH.sub.3                                                                          OCH.sub.3                                           O     H  On-C.sub.3 H.sub.7                                                                  H  H  OCH.sub.3                                                                          OCH.sub.3                                           O     H  CF.sub.3                                                                            H  H  OCH.sub.3                                                                          OCH.sub.3                                           O     H  H     H  CH.sub.3                                                                         OCH.sub.3                                                                          OCH.sub.3                                           S     H  H     H  H  CH.sub.3                                                                           OCH.sub.3                                           S     H  H     H  H  CH.sub.3                                                                           CH.sub.3                                            S     H  H     H  H  OCH.sub.3                                                                          OCH.sub.3                                           S     H  H     H  H  OCF.sub.2 H                                                                        OCH.sub.3                                           S     H  H     H  H  CF.sub.3                                                                           OCH.sub.3                                           S     H  H     H  H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                           S     H  H     H  H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                           S     H  H     H  H  OCF.sub.2 H                                                                        OCF.sub.2 H                                         S     H  H     H  H  CH.sub.3                                                                           OCF.sub.2 H                                         S     H  H     H  H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                 S     H  H     H  H  OCH.sub.3                                                                          SCH.sub.3                                           S(O)  H  H     H  H  CH.sub.3                                                                           OCH.sub.3                                           S(O)  H  H     H  H  CH.sub.3                                                                           CH.sub.3                                            S(O)  H  H     H  H  OCH.sub.3                                                                          OCH.sub.3                                           S(O)  H  H     H  H  OCF.sub.2 H                                                                        OCH.sub.3                                           S(O)  H  H     H  H  CF.sub.3                                                                           OCH.sub.3                                           S(O)  H  H     H  H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                           S(O)  H  H     H  H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                           S(O)  H  H     H  H  OCF.sub.2 H                                                                        OCF.sub.2 H                                         S(O)  H  H     H  H  CH.sub.3                                                                           OCF.sub.2 H                                         S(O)  H  H     H  H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                 SO.sub.2                                                                            H  H     H  H  CH.sub.3                                                                           OCH.sub.3                                           SO.sub.2                                                                            H  H     H  H  CH.sub.3                                                                           CH.sub.3                                            SO.sub.2                                                                            H  H     H  H  OCH.sub.3                                                                          OCH.sub.3                                           SO.sub.2                                                                            H  H     H  H  OCF.sub.2 H                                                                        OCH.sub.3                                           SO.sub.2                                                                            H  H     H  H  CF.sub.3                                                                           OCH.sub.3                                           SO.sub.2                                                                            H  H     H  H  OC.sub.2 H.sub.5                                                                   OCH.sub.3                                           SO.sub.2                                                                            H  H     H  H  C.sub.2 H.sub.5                                                                    OCH.sub.3                                           SO.sub.2                                                                            H  H     H  H  OCF.sub.2 H                                                                        OCF.sub.2 H                                         SO.sub.2                                                                            H  H     H  H  CH.sub.3                                                                           OCF.sub.2 H                                         SO.sub.2                                                                            H  H     H  H  OCH.sub.3                                                                          CH(OCH.sub.3).sub.2                                 SO.sub.2                                                                            H  H     H  H  OCH.sub.3                                                                          SCH.sub.3                                           NH    H  H     H  H  CH.sub.3                                                                           OCH.sub.3                                           NH    H  H     H  H  CH.sub.3                                                                           CH.sub.3                                            NH    H  H     H  H  OCH.sub.3                                                                          OCH.sub.3                                           NCH.sub.3                                                                           H  H     H  H  CH.sub.3                                                                           OCH.sub.3                                           NCH.sub.3                                                                           H  H     H  H  CH.sub.3                                                                           CH.sub.3                                            NCH.sub.3                                                                           H  H     H  H  OCH.sub.3                                                                          OCH.sub.3                                           NC.sub.2 H.sub.5                                                                    H  H     H  H  CH.sub.3                                                                           OCH.sub.3                                           NC.sub.2 H.sub.5                                                                    H  H     H  H  CH.sub.3                                                                           CH.sub.3                                            NC.sub.2 H.sub.5                                                                    H  H     H  H  OCH.sub.3                                                                          OCH.sub.3                                           Ni-C.sub.3 H.sub.7                                                                  H  H     H  H  CH.sub.3                                                                           OCH.sub.3                                           Ni-C.sub.3 H.sub.7                                                                  H  H     H  H  CH.sub.3                                                                           CH.sub.3                                            Ni-C.sub.3 H.sub.7                                                                  H  H     H  H  OCH.sub.3                                                                          OCH.sub.3                                           O     H  H     CH.sub.3                                                                         H  OCH.sub.3                                                                          CH.sub.3                                            O     H  H     CH.sub.3                                                                         H  OCH.sub.3                                                                          OCH.sub.3                                           O     H  H     CH.sub.3                                                                         H  CH.sub.3                                                                           CH.sub.3                                            __________________________________________________________________________

                  TABLE VII                                                       ______________________________________                                         ##STR31##                                                                    L     Q       R.sub.1 R.sub.2                                                                           R.sub.4                                                                            R.sub.5                                                                           R     X.sub.1                                                                            Y.sub.1                         ______________________________________                                        L-1   O       H       H   --   --  H     CH.sub.2                                                                           H                               L-1   O       H       H   --   --  H     CH.sub.2                                                                           CH.sub.3                        L-1   O       H       H   --   --  H     CH.sub.2                                                                           OCH.sub.3                       L-1   O       H       H   --   --  H     CH.sub.2                                                                           Cl                              L-1   O       CH.sub.3                                                                              H   --   --  H     CH.sub.2                                                                           OCH.sub.3                       L-1   O       H       H   --   --  H     O    H                               L-1   O       H       Cl  --   --  H     O    CH.sub.3                        L-1   O       H       H   --   --  H     O    OCH.sub.3                       L-1   O       H       H   --   --  H     O    Cl                              L-1   S       H       H   --   --  H     CH.sub.2                                                                           H                               L-1   S       H       H   --   --  H     CH.sub.2                                                                           CH.sub.3                        L-1   S       H       H   --   --  H     CH.sub.2                                                                           OCH.sub.3                       L-1   S       H       H   --   --  H     CH.sub.2                                                                           Cl                              L-1   S       H       H   --   --  H     O    H                               L-1   S       H       H   --   --  H     O    CH.sub.3                        L-1   S       H       H   --   --  H     O    OCH.sub.3                       L-1   S       H       H   --   --  H     O    Cl                              L-1   S(O)    H       H   --   --  H     CH.sub.2                                                                           H                               L-1   S(O)    H       H   --   --  H     CH.sub.2                                                                           CH.sub.3                        L-1   S(O)    H       H   --   --  H     CH.sub.2                                                                           OCH.sub.3                       L-1   S(O)    H       H   --   --  H     CH.sub.2                                                                           Cl                              L-1   S(O)    H       H   --   --  H     O    H                               L-1   S(O)    H       H   --   --  H     O    CH.sub.3                        L-1   S(O)    H       H   --   --  H     O    OCH.sub.3                       L-1   S(O)    H       H   --   --  H     O    Cl                              L-1   SO.sub.2                                                                              H       H   --   --  H     CH.sub.2                                                                           H                               L-1   SO.sub.2                                                                              H       H   --   --  H     CH.sub.2                                                                           CH.sub.3                        L-1   SO.sub.2                                                                              H       H   --   --  H     CH.sub.2                                                                           OCH.sub.3                       L-1   SO.sub.2                                                                              H       H   --   --  H     CH.sub.2                                                                           Cl                              L-1   SO.sub.2                                                                              H       H   --   --  H     O    H                               L-1   SO.sub.2                                                                              H       H   --   --  H     O    CH.sub.3                        L-1   SO.sub.2                                                                              H       H   --   --  H     O    OCH.sub.3                       L-1   SO.sub.2                                                                              H       H   --   --  H     O    Cl                              L-1   NCH.sub.3                                                                             H       H   --   --  H     CH.sub.2                                                                           H                               L-1   NCH.sub.3                                                                             H       H   --   --  H     CH.sub.2                                                                           CH.sub.3                        L-1   NCH.sub.3                                                                             H       H   --   --  H     CH.sub.2                                                                           OCH.sub.3                       L-1   NCH.sub.3                                                                             H       H   --   --  H     CH.sub.2                                                                           Cl                              L-1   NCH.sub.3                                                                             H       H   --   --  H     O    H                               L-1   NCH.sub.3                                                                             H       H   --   --  H     O    CH.sub.3                        L-1   NCH.sub.3                                                                             H       H   --   --  H     O    OCH.sub.3                       L-1   NCH.sub.3                                                                             H       H   --   --  H     O    Cl                              L-2   O       H       H   H    H   H     CH.sub.2                                                                           OCH.sub. 3                      L-2   O       H       H   H    H   H     O    OCH.sub.3                       L-2   S       H       H   H    H   H     CH.sub.2                                                                           CH.sub.3                        L-2   S       H       H   H    H   H     O    OCH.sub.3                       L-2   SO.sub.2                                                                              H       H   H    H   H     CH.sub.2                                                                           OCH.sub.3                       L-2   SO.sub.2                                                                              H       H   H    H   H     O    CH.sub.3                        L-2   NCH.sub.3                                                                             H       H   H    H   H     O    CH.sub.3                        L-3   O       H       H   H    --  H     O    CH.sub.3                        L-3   S       H       H   H    --  H     CH.sub.2                                                                           OCH.sub.3                       L-3   SO.sub.2                                                                              H       H   H    --  H     O    CH.sub.3                        L-3   NCH.sub.3                                                                             H       H   H    --  H     O    CH.sub.3                        L-1   O       H       H   --   --  CH.sub.3                                                                            O    CH.sub.3                        ______________________________________                                    

                  TABLE VIII                                                      ______________________________________                                         ##STR32##                                                                    L      Q       R.sub.1                                                                              R.sub.2                                                                             R.sub.4                                                                             R.sub.5                                                                           R      Y.sub.1                          ______________________________________                                        L-1    O       H      OCH.sub.3                                                                           --    --  H      CH.sub.3                         L-1    O       H      H     --    --  H      OCH.sub.3                        L-1    O       H      H     --    --  H      CH.sub.3                         L-1    O       H      H     --    --  H      Cl                               L-1    S       H      H     --    --  H      H                                L-1    S       H      H     --    --  H      CH.sub.3                         L-1    S       H      H     --    --  CH.sub.3                                                                             OCH.sub.3                        L-1    S       H      H     --    --  H      Cl                               L-1    S(O)    H      H     --    --  H      OCH.sub.3                        L-1    SO.sub.2                                                                              H      H     --    --  H      H                                L-1    SO.sub.2                                                                              H      H     --    --  H      Cl                               L-1    SO.sub.2                                                                              H      H     --    --  H      CH.sub. 3                        L-1    SO.sub.2                                                                              H      H     --    --  H      OCH.sub.3                        L-1    NCH.sub.3                                                                             H      H     --    --  H      H                                L-1    NCH.sub.3                                                                             H      H     --    --  H      Cl                               L-1    NCH.sub.3                                                                             H      H     --    --  H      CH.sub.3                         L-1    NCH.sub.3                                                                             H      H     --    --  H      OCH.sub.3                        L-2    O       H      H     H     H   H      OCH.sub.3                        L-2    S       H      H     H     H   H      OCH.sub.3                        L-2    SO.sub.2                                                                              H      H     H     H   H      OCH.sub.3                        L-2    CH.sub.3                                                                              H      H     H     H   H      OCH.sub.3                        L-3    O       H      H     H     --  H      OCH.sub.3                        L-3    S       H      H     H     --  H      OCH.sub.3                        L-3    SO.sub.2                                                                              H      H     H     --  H      OCH.sub.3                        L-3    NCH.sub.3                                                                             H      H     H     --  H      OCH.sub.3                        ______________________________________                                    

                  TABLE IX                                                        ______________________________________                                         ##STR33##                                                                    L      Q       R.sub.1 R.sub.2                                                                            R.sub.4                                                                             R.sub.5                                                                           R      Y.sub.1                          ______________________________________                                        L-1    O       H       CH.sub.3                                                                           --    --  H      OCH.sub.3                        L-1    O       CH.sub.3                                                                              H    --    --  H      OCH.sub.3                        L-1    O       H       H    --    --  CH.sub.3                                                                             OCH.sub.3                        L-1    O       H       H    --    --  H      H                                L-1    O       H       H    --    --  H      Cl                               L-1    O       H       H    --    --  H      OCH.sub.3                        L-1    O       H       H    --    --  H      CH.sub.3                         L-1    S       H       H    --    --  H      H                                L-1    S       H       H    --    --  H      Cl                               L-1    S       H       H    --    --  H      CH.sub.3                         L-1    S       H       H    --    --  H      OCH.sub.3                        L-1    S(O)    H       H    --    --  H      H                                L-1    S(O)    H       H    --    --  H      Cl                               L-1    S(O)    H       H    --    --  H      CH.sub.3                         L-1    S(O)    H       H    --    --  H      OCH.sub.3                        L-1    SO.sub.2                                                                              H       H    --    --  H      H                                L-1    SO.sub.2                                                                              H       H    --    --  H      Cl                               L-1    SO.sub.2                                                                              H       H    --    --  H      CH.sub.3                         L-1    SO.sub.2                                                                              H       H    --    --  H      OCH.sub.3                        L-1    NCH.sub.3                                                                             H       H    --    --  H      H                                L-1    NCH.sub.3                                                                             H       H    --    --  H      Cl                               L-1    NCH.sub.3                                                                             H       H    --    --  H      CH.sub.3                         L-1    NCH.sub.3                                                                             H       H    --    --  H      OCH.sub.3                        L-2    O       H       H    H     H   H      OCH.sub.3                        L-3    SO.sub.2                                                                              H       H    H     --  H      OCH.sub.3                        ______________________________________                                    

                  TABLE X                                                         ______________________________________                                         ##STR34##                                                                    L     Q       R.sub.1                                                                              R.sub.2                                                                           R.sub.4                                                                            R.sub.5                                                                           R    X.sub.2                                                                              Y.sub.2                         ______________________________________                                        L-1   O       H      H   --   --  H    CH.sub.3                                                                             SCH.sub.3                       L-1   O       H      H   --   --  H    CH.sub.3                                                                             OCH.sub.3                       L-1   O       H      H   --   --  H    CH.sub.3                                                                             CH.sub.3                        L-1   O       H      H   --   --  H    C.sub.2 H.sub.5                                                                      OCH.sub.3                       L-1   O       H      H   --   --  H    CH.sub.2 CF.sub.3                                                                    OCH.sub.3                       L-1   S       H      H   --   --  H    CH.sub.3                                                                             SCH.sub.3                       L-1   S       H      H   --   --  H    CH.sub.3                                                                             OCH.sub.3                       L-1   S       H      H   --   --  H    CH.sub.3                                                                             CH.sub.3                        L-1   SO.sub.2                                                                              H      H   --   --  H    CH.sub.3                                                                             SCH.sub.3                       L-1   SO.sub.2                                                                              H      H   --   --  H    CH.sub.3                                                                             OCH.sub.3                       L-1   SO.sub.2                                                                              H      H   --   --  H    CH.sub.3                                                                             CH.sub.3                        L-1   NCH.sub.3                                                                             H      H   --   --  H    CH.sub.3                                                                             CH.sub.3                        L-1   NCH.sub.3                                                                             H      H   --   --  H    CH.sub.3                                                                             SCH.sub.3                       L-1   NCH.sub.3                                                                             H      H   --   --  H    CH.sub.3                                                                             OCH.sub.3                       L-2   O       H      H   H    H   H    CH.sub.3                                                                             OCH.sub.3                       L-2   O       H      H   H    H   H    CH.sub.3                                                                             SCH.sub.3                       L-2   S       H      H   H    H   H    CH.sub.3                                                                             OCH.sub.3                       L-2   S       H      H   H    H   H    CH.sub.3                                                                             SCH.sub.3                       L-2   SO.sub.2                                                                              H      H   H    H   H    CH.sub.3                                                                             OCH.sub.3                       L-2   NCH.sub.3                                                                             H      H   H    H   H    CH.sub.3                                                                             OCH.sub.3                       L-3   O       H      H   H    --  H    CH.sub.3                                                                             OCH.sub.3                       L-3   S       H      H   H    --  H    CH.sub.3                                                                             OCH.sub.3                       L-3   SO.sub.2                                                                              H      H   H    --  H    CH.sub.3                                                                             OCH.sub.3                       L-3   NCH.sub.3                                                                             H      H   H    --  H    CH.sub.3                                                                             OCH.sub.3                       ______________________________________                                    

                  TABLE XI                                                        ______________________________________                                         ##STR35##                                                                    L      Q       R.sub.1 R.sub.2                                                                           R.sub.4                                                                             R.sub.5                                                                           R     Y.sub.2                            ______________________________________                                        L-1    O       H       H   --    --  H     OCH.sub.3                          L-1    O       H       H   --    --  H     CH.sub.3                           L-1    S       H       H   --    --  H     OCH.sub.3                          L-1    S       H       H   --    --  H     CH.sub.3                           L-1    SO.sub.2                                                                              H       H   --    --  H     OCH.sub.3                          L-1    SO.sub.2                                                                              H       H   --    --  H     CH.sub.3                           L-1    NCH.sub.3                                                                             H       H   --    --  H     OCH.sub.3                          L-1    NCH.sub.3                                                                             H       H   --    --  H     CH.sub.3                           L-2    O       H       H   H     H   H     OCH.sub.3                          L-2    S       H       H   H     H   H     OCH.sub.3                          L-2    SO.sub.2                                                                              H       H   H     H   H     OCH.sub.3                          L-2    NCH.sub.3                                                                             H       H   H     H   H     OCH.sub.3                          L-3    O       H       H   H     --  H     OCH.sub.3                          L-3    S       H       H   H     --  H     OCH.sub.3                          L-3    SO.sub.2                                                                              H       H   H     --  H     OCH.sub.3                          L-3    NCH.sub.3                                                                             H       H   H     --  H     OCH.sub.3                          ______________________________________                                    

FORMULATIONS

Useful formulations of the compounds of Formula I can be prepared inconventional ways. They include dusts, granules, pellets, solutions,suspensions, emulsions, wettable powders, emulsifiable concentrates andthe like. Many of these may be applied directly. Sprayable formulationscan be extended in suitable media and used at spray volumes of from afew liters to several hundred liters per hectare. High strengthcompositions are primarily used as intermediates for furtherformulation. The formulations, broadly, contain about 0.1% to 99% byweight of active ingredient(s) and at least one of (a) about 0.1% to 20%surfactant(s) and (b) about 1% to 99.9% solid or liquid diluent(s). Morespecifically, they will contain these ingredients in the followingapproximate proportions:

                  TABLE XII                                                       ______________________________________                                                            Weight                                                                Active  Percent*                                                              Ingredient                                                                            Diluent(s)                                                                              Surfactant(s)                                   ______________________________________                                        Wettable Powders                                                                            20-90      0-74      1-10                                       Oil Suspensions,                                                                             3-50     40-95      0-15                                       Emulsions, Solutions,                                                         (including Emulsifiable                                                       Concentrates)                                                                 Aqueous Suspension                                                                          10-50     40-84      1-20                                       Dusts          1-25     70-99     0-5                                         Granules and Pellets                                                                        0.1-95      5-99.9   0-15                                       High Strength 90-99      0-10     0-2                                         Compositions                                                                  ______________________________________                                         *Active ingredient plus at least one of a Surfactant or a Diluent equals      100 weight percent.                                                      

Lower or higher levels of active ingredient can, of course, be presentdepending on the intended use and the physical properties of thecompound. Higher ratios of surfactant to active ingredient are sometimesdesirable, and are achieved by incorporation into the formulation or bytank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook ofInsecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books,Caldwell, N.J., but other solids, either mined or manufactured, may beused. The more absorptive diluents are preferred for wettable powdersand the denser ones for dusts. Typical liquid diluents and solvents aredescribed in Marsden, "Solvents Guide," 2nd Ed., Interscience, New York,1950. Solubility under 0.1% is preferred for suspension concentrates;solution concentrates are preferably stable against phase separation at0° C. "McCutcheon's Detergents and Emulsifiers Annual", MC PublishingCorp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia ofSurface Active Agents", Chemical Publishing Co., Inc., New York, 1964,list surfactants and recommended uses. All formulations can containminor amounts of additives to reduce foaming, caking, corrosion,microbiological growth, etc.

The methods of making such compositions are well known. Solutions areprepared by simply mixing the ingredients. Fine solid compositions aremade by blending and, usually, grinding as in a hammer or fluid energywill. Suspensions are prepared by wet milling (see, for example,Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made byspraying the active material upon preformed granular carriers or byagglomeration techniques. See J. E. Browning, "Agglomeration", ChemicalEngineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer'sHandbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.

For further information regarding the art of formulation, see forexample:

H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, line 16through Col. 7, line 19 and Examples 10 through 41;

R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5, line43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58,132, 138-140, 162-164, 166, 167 and 169-182;

H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 3,line 66 through Col. 5, line 17 and Examples 1-4;

G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc.,New York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., BlackwellScientific Publications, Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwiseindicated.

EXAMPLE 18 Wettable Powder

    ______________________________________                                        1,3-Dihydro-N-- [(4-methoxy-6-methylpyrimidin-2-yl)-                                                     80%                                                aminocarbonyl]benzo[c]furan-4-sulfonamide                                     sodium alkylnaphthalenesulfonate                                                                         2%                                                 sodium ligninsulfonate     2%                                                 synthetic amorphous silica 3%                                                 kaolinite                  13%                                                ______________________________________                                    

The ingredients are blended, hammer-milled until all the solids areessentially under 50 microns, reblended, and packaged.

EXAMPLE 19 Wettable Powder

    ______________________________________                                        1,3-Dihydro-N-- [(4-methoxy-6-methylpyrimidin-2-yl)-                                                     50%                                                aminocarbonyl]benzo[c]furan-4-sulfonamide                                     sodium alkylnaphthalenesulfonate                                                                          2%                                                low viscosity methyl cellulose                                                                            2%                                                diatomaceous earth         46%                                                ______________________________________                                    

The ingredients are blended, coarsely hammer-milled and then air-milledto produce particles essentially all below 10 microns in diameter. Theproduct is reblended before packaging.

EXAMPLE 20 Granule

    ______________________________________                                        Wettable Powder of Examp1e 19                                                                         5%                                                    attapulgite granules   95%                                                    (U.S.S. 20-40 mesh; 0.84-0.42 mm)                                             ______________________________________                                    

A slurry of wettable powder containing ≈25% solids is sprayed on thesurface of attapulgite granules while tumbling in a double-cone blender.The granules are dried and packaged.

EXAMPLE 21 Extruded Pellet

    ______________________________________                                        1,3-Dihydro-N--[(4,6-dimethoxypyrimidin-2-yl)amino-                                                       25%                                               carbonyl]benzo[c]furan-4-sulfonamide                                          anhydrous sodium sulfate    10%                                               crude calcium ligninsulfonate                                                                              5%                                               sodium alkylnaphthalenesulfonate                                                                           1%                                               calcium/magnesium bentonite 59%                                               ______________________________________                                    

The ingredients are blended, hammer-milled and then moistened with about12% water. The mixture is extruded as cylinders about 3 mm diameterwhich are cut to produce pellets about 3 mm long. These may be useddirectly after drying, or the dried pellets may be crushed to pass aU.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S.No. 40 sieve (0.42 mm openings) may be packaged for use and the finesrecycled.

EXAMPLE 22 Oil Suspension

    ______________________________________                                        1,3-Dihydro-N--[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-                                                   25%                                              aminocarbonyl]benzo[c]furan-4-sulfonamide                                     polyoxyethylene sorbitol hexaoleate                                                                         5%                                              highly aliphatic hydrocarbon oil                                                                           70%                                              ______________________________________                                    

The ingredients are ground together in a sand mill until the solidparticles have been reduced to under about 5 microns. The resultingthick suspension may be applied directly, but preferably after beingextended with oils or emulsified in water.

EXAMPLE 23 Wettable Powder

    ______________________________________                                        1,3-Dihydro-N--[(4,6-dimethoxy-1,3,5-triazin-2-yl)-                                                     20%                                                 aminocarbonyl]benzo[c]furan-4-sulfonamide                                     sodium alkylnaphthalenesulfonate                                                                        4%                                                  sodium ligninsulfonate    4%                                                  low viscosity methyl cellulose                                                                          3%                                                  attapulgite               69%                                                 ______________________________________                                    

The ingredients are thoroughly blended. After grinding in a hammer-millto produce particles essentially all below 100 microns, the material isreblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) andpackaged.

EXAMPLE 24 Low Strength Granule

    ______________________________________                                        1,3-Dihydro-N--[(4,6-dimethoxypyrimidin-2-yl)amino-                                                       1%                                                carbonyl]benzo[c]furan-4-sulfonamide                                          N,N--dimethylformamide      9%                                                attapulgite granules        90%                                               (U.S.S. 20-40 sieve)                                                          ______________________________________                                    

The active ingredient is dissolved in the solvent and the solution issprayed upon dedusted granules in a double cone blender. After sprayingof the solution has been completed, the blender is allowed to run for ashort period and then the granules are packaged.

EXAMPLE 25 Aqueous Suspension

    ______________________________________                                        1,3-Dihydro-N--[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-                                                    40%                                             aminocarbonyl]benzo[c]furan-4-sulfonamide                                     polyacrylic acid thickener   0.3%                                             dodecylphenol polyethylene glycol ether                                                                    0.5%                                             disodium phosphate             1%                                             monosodium phosphate         0.5%                                             polyvinyl alcohol            1.0%                                             water                        56.7%                                            ______________________________________                                    

The ingredients are blended and ground together in a sand mill toproduce particles essentially all under 5 microns in size.

EXAMPLE 26 Solution

    ______________________________________                                        1,3-Dihydro-N--[(4,6-dimethoxy-1,3,5-triazin-2-yl)-                                                        5%                                               aminocarbonyl]benzo[c]furan-4-sulfonamide, sodium                             salt                                                                          water                       95%                                               ______________________________________                                    

The salt is added directly to the water with stirring to produce thesolution, which may then be packaged for use.

EXAMPLE 27 Low Strength Granule

    ______________________________________                                        1,3-Dihydro-N--[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-                                                    0.1%                                            aminocarbonyl]benzo[c]furan-4-sulfonamide                                     attapulgite granules         99.9%                                            (U.S.S. 20-40 mesh)                                                           ______________________________________                                    

The active ingredient is dissolved in a solvent and the solution issprayed upon dedusted granules in a double-cone blender. After sprayingof the solution has been completed, the material is warmed to evaporatethe solvent. The material is allowed to cool and then packaged.

EXAMPLE 28 Granule

    ______________________________________                                        1,3-Dihydro-N--[(4,6-dimethoxy-1,3,5-triazin-2-yl)-                                                     80%                                                 aminocarbonyl]benzo[c]furan-4-sulfonamide                                     wetting agent              1%                                                 crude ligninsulfonate salt (containing                                                                  10%                                                 5-20% of the natural sugars)                                                  attapulgite clay           9%                                                 ______________________________________                                    

The ingredients are blended and milled to pass through a 100 meshscreen. This material is then added to a fluid bed granulator, the airflow is adjusted to gently fluidize the material, and a fine spray ofwater is sprayed onto the fluidized material. The fluidization andspraying are continued until granules of the desired size range aremade. The spraying is stopped, but fluidization is continued, optionallywith heat, until the water content is reduced to the desired level,generally less than 1%. The material is then discharged, screened to thedesired size range, generally 14-100 mesh (1410-149 microns), andpackaged for use.

EXAMPLE 29 High Strength Concentrate

    ______________________________________                                        1,3-Dihydro-N--[(4,6-dimethoxypyrimidin-2-yl)amino-                                                        99%                                              carbonyl]benzo[c]furan-4-sulfonamide                                          silica aerogel              0.5%                                              synthetic amorphous silica  0.5%                                              ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce amaterial essentially all passing a U.S.S. No. 50 screen (0.3 mmopening). The concentrate may be formulated further if necessary.

EXAMPLE 30 Wettable Powder

    ______________________________________                                        1,3-Dihydro-N--[(4,6-dimethoxy-1,3,5-triazin-2-yl)-                                                        90%                                              aminocarbonyl]benzo[c]furan-4-sulfonamide                                     dioctyl sodium sulfosuccinate                                                                             0.1%                                              synthetic fine silica       9.9%                                              ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produceparticles essentially all below 100 microns. The material is siftedthrough a U.S.S. No. 50 screen and then packaged.

EXAMPLE 31 Wettable Powder

    ______________________________________                                        1,3-Dihydro-N--[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-                                                   40%                                              aminocarbonyl]benzo[c]furan-4-sulfonamide                                     sodium ligninsulfonate       20%                                              montmorillonite clay         40%                                              ______________________________________                                    

The ingredients are thoroughly blended, coarsely hammer-milled and thenair-milled to produce particles essentially all below 10 microns insize. The material is reblended and then packaged.

EXAMPLE 32 Oil Suspension

    ______________________________________                                        1,3-Dihydro-N--[(4-methoxy-6-methylpyrimidin-2-yl)-                                                      35%                                                aminocarbonyl]benzo[c]furan-4-sulfonamide                                     blend of polyalcohol carboxylic                                                                           6%                                                esters and oil soluble petroleum                                              sulfonates                                                                    xylene                     59%                                                ______________________________________                                    

The ingredients are combined and ground together in a sand mill toproduce particles essentially all below 5 microns. The product can beused directly, extended with oils, or emulsified in water.

UTILITY

Test results indicate that the compounds of the present invention areactive herbicides. They should have utility for broad-spectrum pre-and/or post-emergence weed control in areas where complete control ofall vegetation is desired, such as around fuel storage tanks, ammunitiondepots, industrial storage areas, parking lots, drive-in theaters,around billboards, highway and railroad structures. Alternatively, manyof the subject compounds should be useful for the selectivepost-emergence weed control in crops, especially wheat.

The rates of application for the compounds of the invention aredetermined by a number of factors, including their use as selective orgeneral herbicides, the crop species involved, the types of weeds to becontrolled, weather and climate, formulations selected, mode ofapplication, amount of foliage present, etc. In general terms, thesubject compounds should be applied at levels of around 0.005 to 10kg/ha, the lower rates being suggested for use on lighter soils and/orthose having a low organic matter content, for selective weed control orfor situations where only short-term persistence is required.

The compounds of the invention may be used in combination with any othercommercial herbicide; examples of which are those of the triazine,triazole, uracil, urea, amide, diphenylether, carbamate and bipyridyliumtypes.

The herbicidal properties of the subject compounds were discovered in agreenhouse test. The test procedure and results follow.

TEST A

Seeds of crabgrass (Digitaria sp.), barnyardgrass (Echinochloacrusgalli), wild oats (Avena fatua), sicklepod (Cassia obtusifolia),morningglory (Ipomoea sp.), cocklebur (Xanthium sp.), sorghum, corn,soybean, sugar beet, cotton, rice, wheat and purple nutsedge (Cyperusrotundus) tubers were planted and treated pre-emergence with the testchemicals dissolved in a non-phytotoxic solvent. At the same time, thesecrop and weed species were treated with a soil/foliage application. Atthe time of treatment, the plants ranged in height from 2 to 18 cm.Treated plants and controls were maintained in a greenhouse for sixteendays, after which all species were compared to controls and visuallyrated for response to treatment. The ratings, summarized in Table A, arebased on a numerical scale extending from 0=no injury, to 10=completekill. The accompanying descriptive symbols have the following meanings:

C=chlorosis/necrosis;

E=emergence inhibition;

G=growth retardation;

H=formative effects; and

U=unusual pigmentation.

It will be seen from the data for some of the compounds tested thatwheat is tolerant of rates of application which provide excellentcontrol of several problem weed species. Therefore, compounds fromwithin the scope of the invention should be useful for selectivepost-emergence weed control in cereal crops, such as wheat. ##STR36##

                                      TABLE A                                     __________________________________________________________________________                                               Cmpd.                                                                             Cmpd.                                                                             Cmpd.                                                                             Cmpd.                                                                             Cmpd.                      Cmpd. 1                                                                            Cmpd. 2                                                                            Cmpd. 3                                                                            Cmpd. 4                                                                            Cmpd. 5                                                                            Cmpd. 6                                                                            Cmpd. 7                                                                            8   9   10  11  12                 Rate g/ha                                                                             50   50   50   50   50   50   50   50  50  50  50  50                 __________________________________________________________________________    POST-EMERGENCE                                                                Morningglory                                                                          6C,9G                                                                              5C,9G                                                                              9C   4C,8H                                                                              2C,5G                                                                              2C,6G                                                                              2G   2G  0   2G  3C,7H                                                                             0                  Cocklebur                                                                             9C   2C,8H                                                                              10C  8H   3C,9H                                                                              3C,8H                                                                              2C,6G                                                                              2C,9H                                                                             1C,3G                                                                             2G  3C,9H                                                                             0                  Sicklepod                                                                             9C   7G   5C,9G                                                                              4C,8H                                                                              2C,2G                                                                              2C   1C   1C  0   0   3C,7G                                                                             0                  Nutsedge                                                                              9C   4C,9G                                                                              5G   4G   2C,8G                                                                              2C,8G                                                                              0    0   0   0   0   0                  Crabgrass                                                                             8G   5H   2C,7G                                                                              3G   2C   0    0    2G  0   0   0   0                  Barnyardgrass                                                                         4C,9H                                                                              2C,9H                                                                              6C,9H                                                                              9H   5C,9H                                                                              3C,8H                                                                              0    2C,8H                                                                             0   0   0   0                  Wild Oats                                                                             5C,9G                                                                              2G   4C,9G                                                                              0    0    0    0    1C  0   0   0   0                  Wheat   9C   2G   6C,9G                                                                              0    0    0    0    1C  0   0   0   0                  Corn    5U,9C                                                                              2C,9H                                                                              6U,9G                                                                              7H   1C,9G                                                                              3C,7H                                                                              2C,7H                                                                              2C,9G                                                                             1C,1H                                                                             0   0   0                  Soybean 5C,9G                                                                              5C,9G                                                                              9C   6C,9G                                                                              3C,8G                                                                              2C,8G                                                                              1C,1H                                                                              2C,8G                                                                             1C,5G                                                                             0   2C,9G                                                                             0                  Rice    6C,9G                                                                              2C,5G                                                                              9C   6C,9G                                                                              2C,5G                                                                              2C,5G                                                                              2G   2C,8G                                                                             7G  0   0   0                  Sorghum 2C,9H                                                                              2C,6H                                                                              7U,9G                                                                              9G   2C,9G                                                                              2C,6H                                                                              2G   2C,8H                                                                             2C,8H                                                                             0   3C,9H                                                                             0                  Sugar beet                                                                            9C   9C   9C   3C,6H                                                                              3C,8H                                                                              3C,8G                                                                              6G   3C,9G                                                                             2C,8G                                                                             1C  9C  0                  Cotton  4C,9G                                                                              3C,9G                                                                              9C   5C,9G                                                                              4C,8H                                                                              3C,9G                                                                              2G   1C  5G  0   4C,9H                                                                             0                  __________________________________________________________________________    PRE-EMERGENCE                                                                 Morningglory                                                                          9G   9G   9G   9H   8G   2C,7G                                                                              --   6G  3C,6H                                                                             0   3C,8G                                                                             0                  Cocklebur                                                                             9H   9H   9H   9H   9G   9G   4G   1H  9H  0   2C,2H                                                                             0                  Sicklepod                                                                             9G   9G   9G   9G   8G   8G   0    8G  2C,8G                                                                             0   3C,7G                                                                             0                  Nutsedge                                                                              10E  10E  7G   7G   2G   10E  0    0   0   0   5G  0                  Crabgrass                                                                             4C,9G                                                                              4C,9G                                                                              5C,9G                                                                              3C,7G                                                                              0    0    0    0   0   0   0   0                  Barnyardgrass                                                                         5C,9H                                                                              9H   5C,9H                                                                              3C,9H                                                                              5G   2C,5G                                                                              0    3G  1H  0   2C,4G                                                                             0                  Wild Oats                                                                             5C,9H                                                                              4C,9G                                                                              4C,9G                                                                              2C,9G                                                                              2C,9G                                                                              4G   0    0   0   0   4G  0                  Wheat   7C,9H                                                                              4C,9G                                                                              5C,9G                                                                              8G   0    0    0    0   0   0   0   0                  Corn    10E  2U,9G                                                                              3U,9G                                                                              4C,9G                                                                              2C,9G                                                                              2C,8H                                                                              2G   6G  4G  0   2C,7G                                                                             0                  Soybean 9H   3C,8H                                                                              9H   4C,8H                                                                              2C,6G                                                                              2C,6G                                                                              0    2C,5G                                                                             1C  0   3C,4H                                                                             2C                 Rice    10E  10E  10E  10E  3C,6G                                                                              3C,8G                                                                              2C   3C,5G                                                                             2C,5G                                                                             0   3C,6G                                                                             0                  Sorghum 10H  2U,9G                                                                              6C,9H                                                                              2C,9H                                                                              3C,8G                                                                              3C,9H                                                                              2C,3G                                                                              3C,8G                                                                             2C,5G                                                                             0   3C,9H                                                                             0                  Sugar beet                                                                            10E  10E  9G   9G   2C,9G                                                                              3C,9G                                                                              6G   8H  7G  0   9C  0                  Cotton  9G   9G   9G   9G   8G   8G   2G   1C  7G  0   8H  0                  __________________________________________________________________________

What is claimed is:
 1. A compound having the formula: ##STR37## where##STR38## Q is O, S(O)_(n) or NR₃ ; n is 0, 1 or 2;R₁ is H, CH₃, Cl orF; R₂ is H, Cl, Br, C₁ -C₃ alkoxy or CF₃ ; R₃ is H or C₁ -C₄ alkyl; R₄is H or CH₃ ; R₅ is H or CH₃ ; R₆ is H, Cl or F; R₇ is H, Cl or F; R₈ isH, Cl or F; R is H or CH₃ ; A is ##STR39## X is F, Cl, Br, C₁ -C₂ alkyl,C₁ -C₂ alkoxy, OCF₂ H or CF₃ ; Y is H, NH₂, NHCH₃, N(CH₃)₂, C₁ -C₄alkyl, C₁ -C₄ alkyl substituted with 1-3 atoms of (a) F, (b) Cl or (c)Br, CH₂ OCH₃, CH₂ OC₂ H₅, C₁ -C₄ alkoxy, C₁ -C₂ alkylthio, C₃ -C₄alkenyloxy, C₃ -C₄ alkynyloxy, OCH₂ CH₂ OCH₃, OCH₂ CH₂ F, OCH₂ CH₂ Cl,OCH₂ CH₂ Br, OCH₂ CF₃, CH(OCH₃)₂, CH(OC₂ H₅)₂, ##STR40## or GCF₂ T; G isO or S; T is H, CHClF, CHBrF, CF₂ H or CHFCF₃ ; Z is CH;provided that:(1) when X is F, Cl or Br, then Y is NH₂, NHCH₃, N(CH₃)₂, CH₃, OCH₃ orOCF₂ H; and (2) when R₁ is F or Cl, then R₆, R₇ and R₈ are the same asR₁ and Q is O or S; and when R₁ is H or CH₃, then R₆, R₇ and R₈ areH;and their agriculturally suitable salts.
 2. A compound of claim 1where L is L-1.
 3. A compound of claim 2 where R is H, R₁ is H and R₂ isH.
 4. A compound of claim 3 where X is Cl, CH₃, OCH₃ or OCF₂ H and Y isCH₃, OCH₃, OCH₂ CH₃, CH₂ OCH₃, CH(OCH₃)₂ or GCF₂ T where G is O and T isH.
 5. The compound of claim 1 which is1,3-dihydro-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]benzo[c]furan-4-sulfonamide.6. The compound of claim 1 which is1,3-dihydro-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]benzo[c]furan-4-sulfonamide.7. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 1and at least one of the following: surfactant, solid or liquid diluent.8. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 2and at least one of the following: surfactant, solid or liquid diluent.9. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 3and at least one of the following: surfactant, solid or liquid diluent.10. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of a compound of claim 4and at least one of the following: surfactant, solid or liquid diluent.11. A composition suitable for controlling the growth of undesiredvegetation which comprises an effective amount of the compound of claim5 and at least one of the following: surfactant, solid or liquiddiluent.
 12. A composition suitable for controlling the growth ofundesired vegetation which comprises an effective amount of the compoundof claim 6 and at least one of the following: surfactant, solid orliquid diluent.
 13. A method for controlling the growth of undesiredvegetation which comprises applying to the locus to be protected aneffective amount of a compound of claim
 1. 14. A method for controllingthe growth of undesired vegetation which comprises applying to the locusto be protected an effective amount of a compound of claim
 2. 15. Amethod for controlling the growth of undesired vegetation whichcomprises applying to the locus to be protected an effective amount of acompound of claim
 3. 16. A method for controlling the growth ofundesired vegetation which comprises applying to the locus to beprotected an effective amount of a compound of claim
 4. 17. A method forcontrolling the growth of undesired vegetation which comprises applyingto the locus to be protected an effective amount of the compound ofclaim
 5. 18. A method for controlling the growth of undesired vegetationwhich comprises applying to the locus to be protected an effectiveamount of the compound of claim 6.